Thermosetting polysulfones

ABSTRACT

Class of high performance thermosetting materials composed of polyarylene polyether resins having each of their ends capped with a monovalent unsaturated organo radical. The end-capped polyarylene polyether resins have the formula: 
     
         Z--polyarylene polyether chain--Z&#39; 
    
     wherein Z and Z&#39; are each a monovalent unsaturated organo radical. Usually Z and Z&#39; are alkylene, aralkylene or cycloalkylene moieties. The end-capped polyarylene polyethers can be cured as is or in the presence of one or more unsaturatd comonomers to afford homopolymers or copolymers, respectively. Such cured systems exhibit high glass transition temperatures, good tensile properties, excellent electric and alkali resistance and improved stress cracking resistance. End-terminated polysulfone resins having molecular weight of 5,000 to 15,000 are especially advantageous. The properties exhibited by the vinyl/allyl terminated oligomers are useful in fields which require high temperature performance, excellent solvent resistance and good fabrication characteristics. Specific areas of application include high performance molded products for appliances and electronics, high temperature laminates and adhesives and protective and insulative coatings.

This is a continuation of application Ser. No. 775,713, filed Sept. 16,1985, abandoned, which is a continuation of Ser. No. 659,509, filed Oct.11, 1984, abandoned, which is a continuation of Ser No. 563,267, filedDec. 20, 1983, which is a continuation of Ser. No. 393,768, filed June20, 1982, abandoned.

BACKGROUND OF THIS INVENTION

1. Field Of This Invention

The invention relates to thermosetting end-capped polyarylenepolyethers, including end-capped polyarylene polyethers, processes ofpreparing and using such resins, composites containing such resins, andhomopoLymers and copolymers prepared from such resins.

2. Prior Art

Thermoplastic polyarylene polyethers are known. Thermoplastic silaneend-capped polyarylene polyethers and thermoplasticpolysiloxane-polyarylene polyether copolymers are also known.

BROAD DESCRIPTION OF THE INVENTION

An object of the invention is to provide a new and useful class of highperformance end-capped polyarylene polyethers, particularly end-cappedpolysulfones. Another object of the invention is to provide compositionscontaining and copolymers produced from such polyarylene polyethers andcomonomers. Another object of this invention is to provide homopolymersprepared from such polyarylene polyethers. A further object of theinvention is to provide processes for preparing and using suchpolyarylene polyethers, compositions, homopolymers and copolymers. Astill further object of the invention is to provide a composite of asubstrate and such polyarylene polyethers, homopolymers and copolymers.Other objects and advantages of the invention are set out herein or areobvious herefrom to one ordinarily skilled in the art.

The objects and advantages of the invention are achieved by thethermosetting polyarylene polyethers and so forth of the invention.

The thermosetting, monovalent unsaturated organo end-capped polyarylenepolyethers of the invention differ from the known thermoplasticpolyarylene polyethers and the known silane end-capped polyarylenepolyethers most significantly in that the compositions of the inventionhave reactive, monovalent, unsaturated organo end-capping groups.

In its broadest sense, the invention involves end-capped polyarylenepolyethers having the formula:

    Z--polyarylene polyether chanin--Z'

wherein Z and Z' are each a monovalent unsaturated organo moiety. Thepolyarylene polyether chain can be substituted or unsubstituted. Theend-capped resins of the invention are a class of organic resins havingetheric oxygen valently connecting together aromatic nuclei or residueof aromatic compounds. These end-capped resins are appropriately termedend-capped polyarylene polyethers resins.

A preferred class of compositions that are within the scope of theinvention are the thermosetting end-capped polyarylene polyether resinshaving the formula:

    Z--O--E'--O--E).sub.n OZ'

wherein n is a positive number, Z and Z' are each a monovalentunsaturated organo moiety, E is the residue after removal of thehydroxyl groups of a dihydric phenol, and E' is the residue afterremoval of the two activated halo groups of an aromatic compound havingtwo activated halo substituents. The residues represented by E and E'can be unsubstituted or substituted beyond the already defined degree.These thermosetting resins can be produced by reacting an alkali metalphenoxide end-capped polyarylene polyether with a monovalent,monohalo-substituted, unsaturated organo compound. Preferably n is 2 to300; and preferably Z and Z' are each an alkylene, aralkylene orcycloalkylene moiety.

Another preferred class of compositions that are within the scope of theinvention are the thermosetting end-capped polyarylene polyetherogliomers or resins having the formula:

    Z--O--Ar).sub.n OZ'

wherein n is a positive number, Z and Z' are each a monovalentunsaturated organo moiety, and Ar is a divalent aromatic group that canbe the same or different from one --O--Ar-- group to the next, and inwhich each Ar group is bonded to the connecting oxy groups througharomatic carbon atoms. The aromatic group represented by Ar can besubstituted or unsubstituted. These thermosetting resins can be producedby reacting an alkali metal phenoxide end-capped polyarylene polyetherwith a monovalent, monohalo-substituted, unsaturated organo compound.Preferably n is 2 to 300; and preferably Z and Z' are each an alkylene,aralkylene or cycloalkylene moiety.

The polyarylene polyether chain, particularly the benzenoidconstituents, can contain inert substituents such as halogens (e.g.,chlorine, bromide and fluorine) alkyl groups having from 1 to 4 carbonatoms and alkoxy groups having 1 to 4 carbon atoms.

The end-capped polyarylene polyether resins of the invention haveexcellent strength and toughness properties as well as outstandingthermal oxidative and chemical stability. They find wide utility in theproduction of shaped and molded articles where such properties arenecessary and are highly desirable and also in the preparation of filmand fiber products which have excellent mechanical properties

Heat-hardenable resins can be blended with thermosetting, end-cappedpolyarylene polyether resins of this invention to yield useful mixtures.

The preferred class of end-capped thermosetting resins of the inventionare those polysulfones where the thermosetting polyarylene polyetherresin is composed of recurring units having the formula: ##STR1##wherein R is hydrogen, lower alkyl, lower aryl and halogen substitutedlower alkyl and lower aryl groups. Most preferably R is methyl. Thelower alkyl groups have from 1 to 4 carbon atoms.

As often used herein, the polysulfone-vinyl reactive resins or PSF-VRare the above end-capped resins when R is methyl and the end-cappingmoieties are alkylene, aralkylene or cycloalkylene moieties. Other timesherein the phrase polysulfone-vinyl reactive resins (PSF-VR) is used asa shorthand reference broadly for the end-capped polyarylene polyetherresins.

The ability of polysulfone-vinyl reactive resins to be cured byconventional techniques and their ability to copolymerize with a varietyof commercially available, inexpensive comonomers, make them animportant class of new thermoset resins. Of particular importance is thepolysulfone-vinyl reactive styrene binder system which not only forms atrue solution in any proportion but also yields a copolymer of uniform,well-defined properties. It can be formulated, processed and cured likean unsaturated polyester resin to impart higher use temperatures, bettermechanical and electrical properties, and, above all, improved chemicalresistance to strong alkaline environment.

The polysulfone-vinyl reactive resins of the invention are particularlyuseful as (1) corrosion resistance matrix resins or additives, (2)powder coatings, (3) magnet wire coatings, (4) photocurable andradiation coatings and (5) in fiber reinforced structural composites.

The thermoset vinyl benzyloxy end-capped polysulfones in coating form onmetal sheets and the like are highly resistant to the solvent action toacetone and chlorinated hydrocarbons, such as, methylene chloride. Suchcoatings are also highly resistant to hot alkali solutions.

A thermoset or baked coating of the allyl end-capped polysulfones on ametal or glass substrate is readily removable or strippable oncesubjected to hot detergent solutions. This property means strippablecoating applications to protect glass substrates, particularly to hotalkali solutions for the thermoset allyl-terminated polysulfone coatingsof the invention. Similarly, metal protective coatings, such as, metalstrip and prime coatings, can coatings, wire magnet coatings and pipeliner coatings are also applications for the thermoset allyl-terminatedpolysulfones of the invention.

The thermoset vinylbenzyloxy end-capped polysulfone (10,000 molecularweight) had significant resistance to the solvent action oftrichloroethylene, which is important in some electrical applications.

The end-capped polyarylene polyethers of the invention have the sameadvantages and uses as the subgroup end-capped polysulfones of theinvention.

The invention includes the homopolymers of the end-capped polyarylenepolyether having the formula:

    Z--polyarylene polyether chain--Z'

wherein Z and Z' are each a monovalent unsaturated organo moiety. Thepolyarylene polyether chain can be substituted or unsubstituted. Thehomopolymer can be prepared from any of the vinyl reactive end-cappedpolyarylene polyethers taught or described herein.

A preferred class of homopolymers which are within the scope of theinvention are the homopoIymers of the end-capped polyarylene polyethershaving the formula:

    Z--O--E'--O--E).sub.n OZ'

wherein n is 2 to 300, Z and Z' are each a monovalent unsaturated organomoiety, E is the residue after removal of the hydryoxyl groups of adihydric phenol and E' is the residue after removal of the two activatedhalo groups of an aromatic compound having two activated halosubstituents. The residues represented by E and E' being unsubstitutedor substituted beyond the already defined degree.

Another preferred class of copolymers which are within the scope of theinvention are the homopolymers of an end-capped polyarylene polyethershaving the formula:

    Z--O--Ar).sub.n OZ'

wherein n is 2 to 300, Z and Z' are each a monovalent unsaturated organomoiety, and Ar is a divalent aromatic group that can be the same ordifferent from one --O--Ar-- group to the next, and in which each Argroup is bonded to the connecting oxy groups through aromatic carbonatoms. The aromatic group represented by Ar being substituted orunsubstituted.

As desired, monomer (B) can have one, two, three or more reactive vinylgroups, depending upon the type of copolymer wanted, speed and cost ofcuring, etc.

The invention also includes the process of preparing such homopolymersby homopolymerizing the end-capped polyarylene polyether monomer of theinvention. The polymerization is effectively conducted in the presenceof a free radical initiator, with concurrent heat application beingpreferred. Polymerization can also be effected by means of actinicradiation, such as ultraviolet light.

The invention further includes the copolymers comprised of:

(A) at least one monomer which is an end-capped polyarylene polyetherhaving the formula:

    Z--polyarylene polyether chain--Z'

wherein Z and Z' are each a monovalent unsaturated organo moiety, thepolyarylene polyether chain being substituted or unsubstituted; and

(B) at least one monomer having at least one monovalent unsaturatedorgano moiety. The copolymer can be prepared using any of the vinylreactive end-capped polyarylene polyethers taught or described herein.

A preferred class of copolymers which are within the scope of theinvention are those wherein on monomer (B) the monovalent unsaturatedorgano moiety is an alkylene, aralkylene or cycloalkylene moiety.

Preferably monomer (B) contains at least one reactive vinyl group R₇ R₈C═CR₉ --, reactive vinylidene group R₇ R₈ C═C═C--, and/or reactivevinylene group --CR₁₀ ═CR₁₁ --. In such formula R₇, R₈, R₉, R₁₀ and R₁₁each is (a) hydrogen, (b) alkyl having 1 to 4 carbon atoms, (c) alkoxyhaving 1 to 4 carbon atoms, (d) alkylcarboxy having 2 to 12 carbonatoms, (e) aryl having 6 to 10 carbon atoms, (f) alkoxycarbonyl having 2to 12 carbon atoms, (g) substituted aryl having 6 carbon atom and beingsubstituted with at least one halogen, nitrile, alkyl having 1 to 4carbon atoms, and/or alkoxy having 1 to 4 carbon atoms, (h) aralkylwherein the alkyl has 1 to 4 carbon atoms and the aryl has 6 to 10carbon atoms, (i) substituted aralkyl wherein the alkyl has 1 to 4carbon atoms, the aryl has 6 to 10 carbon atoms and the substituents arehalogen, alkyl having 1 to 4 carbon atoms, nitrile and/or alkoxy having1 to 4 carbon atoms, (j) substituted alkyl having 1 to 4 carbon atomsand being substituted with nitrile, halogen and/or alkoxy having 1 to 4carbon atoms, (k) substituted alkylcarboxy having 2 to 12 carbon atomsand substituted with halogen, and/or nitrile, or (1) substitutedalkoxycarbonyl having 2 to 12 carbon atoms and substituted with halogen,and/or nitrile. Most preferably monomer (B) is styrene.

The invention still further includes the process of preparing suchcopolymers by copolymerizing the end-capped polyarylene polyethermonomer (A) of the invention and monomer (B) (described above). Thepolymerization is effectively conducted in the presence of a freeradical initiator, with concurrent heat application being preferred.Polymerization can also be effected by means of actinic radiation, suchas, ultraviolet light. Preferably, monomer (A) and monomer (B) arepresent in approximately equal stoichiometric amounts, althougheffectively the molar ratio of monomer (A) to monomer (B) is between 4to 1 and 0.8 to 1.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:

FIG. 1 is a graph of methylene chloride solubility curves for certainplated substrates;

FIG. 2 is a graph of a methylene chloride solubility curve for certainplated substrates;

FIG. 3 is a graph of the charge ratio versus the reduced viscosity; and

FIG. 4 is a graph of the glass transition temperature versus the reducedviscosity.

DETAILED DESCRIPTION OF THE INVENTION

Basically, the end-capped high molecular weight polyarylene polyetherresins of the present invention are the linear thermosetting reactionproducts of an alkali metal double salt of a dihydric phenol and adihalobenzenoid compound, the thermosetting resins then being end-cappedwith mnovalent unsaturated organo compounds. Usually a residuum of adihydric phenol and a residuum of a benzenoid compound are both valentlybonded to the ether oxygen through aromatic carbon atoms.

One convenient method of producing the compositions having the formulae:

    Z--O--E'--O--E).sub.n OZ'

or

    Z--O--Ar).sub.n OZ'

wherein Z, Z', E, E', Ar and n are the same as defined above, is thefollowing:

Dihydric phenol, such as, 2,2-bis(4-hydroxyphenyl)propane("bisphenol-A"), is dissolved in a solvent such as a mixture ofmonochlorobenzene and dimethyl sulfoxide. The dihydric phenol isconverted to the alkali metal salt by adding an alkali metal hydroxide,such as, sodium hydroxide, an alkali metal hydride, an alkali metalhydroxide, an alkali metal alkoxide or an alkali metal alkyl compound,and removing the water of condensation by azeotropic distillation. Anaromatic compound having two activated halo substituents is added to thealkali metal salt. 4,4'-Dichlorodiphenyl sulfone is illustrative of sucharomatic compounds. The dihalo aromatic compound is used in a controlledproportion so that there will be a stoichiometric excess of the alkalimetal salt. The dihalo aromatic compound and the alkali metal salt arereacted to form a linear polyarylene-polyether chain having alkali metalsalt end groups. This compound is then reacted with an appropriateend-capping agent, such as, allyl chloride, to form a monovalentunsaturated organo end-capped polyarylene-polyether, which is recoveredby coagulating the solution in anhydrous methanol or anhydrous isopropylalcohol.

The dihydric phenol used can be a mononuclear compound such ashydroquinone or resorcinol, which may be substituted with an inertsubstituent such as alkyl, alkoxy or halo (with the allyl having 1 to 4carbon atoms). In the case of hydroquinone and the like, a process usingK₂ CO₃ in dimethylacetamide is used wherein the monomers (hydroquinone,4,4'-dichlorodiphenyl sulfone and K₂ CO₃) are charged into thedimethylacetamide (sulfolane is also useful), and the water of reactionis removed azeotropically with toluene or the like. The dihydric phenolcan also be a polynuclear phenol. Examples of polynuclear phenols arep,p-biphenol, naphthalene diol, alkane bisphenols such asbis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl) propane,bisphenol sulfones such as bis(4-hydroxyphenyl) sulfone, the bisphenolsulfides such as bis(4-hydroxyphenyl) sulfide, the bisphenol ethers suchas bis(4-hydroxyphenyl) ether, and the bisphenol ketones such asbis(4-hydroxyphenyl) ketone. The preferred dihydric phenols arehydroquinone, bisphenol-A, p,p'-biphenol and bis(4-hydroxyphenyl)sulfone.

The second class of compounds used are aromatic compounds that have twoactivated halo substitutents. The halo substituents are activated sothat, in the absence of a catalyst, the aromatic compound can react withalkali metal phenoxide to form an ether. As is well known in the art,one way to activate the halo substituents is to have an inert electronwithdrawing group ortho or para to the two halo groups. Thehalo-substituted aromatic compound can be a mononuclear compound, suchas, 1,2,4,5-tetrabromobenzene, 1,2,4,5-tetrachlorobenzene, 2,4- and2,6-dichlorobenzonitrile, hexachlorobenzene and1,4-dibromo2,3,5,6-tetrachlorobenzene, or a polynuclear compound, suchas, 4,4'-dichlorodiphenyl sulfone, 4,4'-bis(4-chlorophenylsulfonyl)biphenyl, 4,4 '-dichlorodiphenyl ketone, 3,4,5,3',4',5'-hexachlorobiphenyl and 4,4'-dibromo-3,5,3',5'-tetrachlorobiphenyl.

Other useful and illustrative dihydric phenols and aromatic compoundsthat contain two activated halo substituents are disclosed in U.S. Pat.Nos. 3,539,656, 3,539,657, 3,355,272, 3,634,354, 3,928,295 and3,764,583, the pertinent portions of which are incorporated herein byreference.

The foregoing outline of a process for producing the above-identifiedcompositions can be represented by the sequence of reaction stepspresented below in which HO-E-OH represents the dihydric phenol andCl--E'--Cl represents the dihalo aromatic compound: ##STR2##

In the above sequence of reaction steps (1), (2) and (3), the dihydricphenol is preferably employed in a stoichiometric excess over the dihaloaromatic compound. Preferably from about 1.02 to about 1.16 moles ofdihydric phenol is employed per mole of the dihalo aromatic compound.Within this range of properties, the reduced viscosities in chloroformat 25° C. and at a concentration of 0.2 gram of polymer per 100milliliters of solution, of the polyarylene polyethers and theend-capped polymers derived therefrom, usually will be within the rangeof from about 0.1 to 0.5 dl/g. (Reduced viscosity is determined by theprocedure of ASTM-D-2857.) Proportions outside this range can also beused in some cases when it is desired to produce end-capped polymers ofeither higher or lower molecular weights. (dg/g means deciliter pergram.)

The above sequence of reaction steps (1), (2) and (3) is the mostconvenient way to produce the above-identified compositions. However,variations of the procedure are well within the skill of the art and arecontemplated by this invention. For instance, reaction step (2) can becarried out with an excess of the dihalo compound (the preferredproportion of stoichiometric excess being the same as that given abovefor the dihydric phenol), followed by an alkaline hydrolysis reaction toconvert the halo substituent to alkali metal phenoxide. Then, afterazeotropic removal of water, the product is subjected to reaction step(3). Alternatively, the "single salt process" can be employed (e.g. asdescribed in British Pat. No. 1,369,156) to produce a polyarylenepolyether terminated at one end by a halo substituent and at the otherby alkali metal phenoxide. Upon alkaline hydrolysis of the halo group,followed by dehydration, the product can then be subjected to Reaction(3), as described herein.

In the first step, that is, reaction step (1), the dihydric phenol isconverted to the corresponding alkali metal salt. Two moles of alkalimetal hydroxide, such as sodium hydroxide or potassium hydroxide, arereacted per mole of dihydric phenol. Almost exactly stoichiometricquantities should be used. This reaction is carried out in a solventsystem that permits azeotropic removal of the water of condensation. Amixture of monochlorobenzene (MCB) and dimethyl sulfoxide (DMSO) isexcellent for this purpose. The DMSO is used as the solvent, and MCB isan azeotroping agent. Other useful solvents include dimethylacetamide(DMAC), and other useful azeotroping agents include chlorinatedbenzenes, benzene, toluene, and xylene. The condensation reaction toproduce the alkali metal phenoxide normally is conducted from about 120to about 240 minutes at a temperature of from about 110° to about 132°C. While a much broader temperature range can be used, the above one isthe most convenient.

After the water of condensation has been removed azeotropically, thedihalo aromatic compound is added to the reaction mixture to carry outreaction step (2). This reaction is carried out at an elevatedtemperature, for example, from about 150° C. to about 170° C., for aperiod of from about 60 to about 120 minutes.

Upon completion of reaction step (2), a polyarylene polyether havingalkali metal phenoxide end groups is produced. This composition isreacted with a monovalent unsaturated organo compound to produce theend-capped polyarylene polyether resins of the invention.

Generally the monovalent unsaturated organo moiety is selected from thegroup consisting of: ##STR3## wherein R₁, R₂ and R₃ each is hydrogen, analiphatic hydrocarbon radical containing 1 to 20 carbon atoms, analicyclic hydrocarbon radical containing 1 to 20 carbon atoms or anaromatic radical, and R₄, R₅ and R₆ each is a divalent alkylene radicalcontaining 1 to 20 carbon atoms, a divalent arylene radical containing 6to 10 carbon atoms or a divalent cycloalkylene radical containing 3 to 8carbon atoms. Preferably R₁, R₂ and R₃ each is hydrogen, an alkylradical having 1 to 8 carbon atoms, an aryl radical, an aralkyl radical,an alicyclic radical having 3 to 8 carbon atoms or a bicyclic radical.Preferably R₄, R₅ and R₆ each is a divalent alkylene radical having 1 to8 carbon atoms. Typical aromatic radicals are benzyl, phenyl andnaphthyl. Typical alkyl radicals are methyl, ethyl, 2-propyl, 1-propyl,1-butyl, 2-methyl-1-propyl, 2-butyl, 1-pentyl, 3-metyl-1-butyl,2-pentyl, 3-pentyl, 3-methyl-2-butyl, 1-hexyl, 2-ethyl-1-butyl,2-metyl-1pentyl, 3-methyl-1-pentyl, 2,3-dimethyl-1-butyl,3-methyl-2pentyl, 4-methyl-2-pentyl, 2,3-dimethyl-2-butyl, 1-heptyl,2,4-dimethyl-3-pentyl, 1-octyl, 2-octyl, 1-dodecyl, 1-octadecyl and1-hexadecyl. Examples of aromatic radicals are benzyl, methyl benzyl,o-, m- and p-dimethylbenzyl, ethylbenzyl, trimethyl benzyl,n-propylbenzyl and isopropylbenzyl. Examples of alicyclic andbialicyclic radicals are cyclobutyl, cyclopropyl methyl, cyclopropyl,cyclopentyl, cyclopentyl methyl, cyclohexyl, cyclohexyl methyl andcyclooctyl. Examples of divalent alkylene radicals are --CH₂ --, --CH₂CH₂ --, --(CH₂)₃ --, --(CH₂)₅₋, ##STR4## and --(CH₂)₁₂ --. Examples ofdivalent arylene radicals are --C₆ H₄ -- (o, m and p), and --C₁₀ H₆ --.Examples of divalent cycloalkylene radicals are ##STR5##

The preferred halide end-capping agents are allyl chloride,2-chloroethylacrylate, 2-chloroethylmethacrylate,chloromethyldimethylvinylsilane, vinyl benzyl chloride and 2-chloroethylvinyl ether.

Examples of useful halides for end-capping are: allyl chloride (CH₂═CH--CH₂ Cl), allyl fluoride, allyl bromide, 1-propenyl chloride (CH₃CH═CHCl), 1-propenyl fluoride, 1-propenyl bromide, CH₃ CH═CHCH₂ Cl, CH₂═CHCH₂ CH₂ Cl, CH₂ ═CHCH₂, CH₂ F, CH₂ ═CH(CH₂)₃ Cl, CHhd 2═CHCH₂ CH₂ CH₂Cl, CH₃ CH═CHCH₂ CH₂ Cl, CH₂ ═C(CH₃)CH₂ CH₂ Cl, CH₂ ═CHCH₂ CH₂ CH₂ CH₂Cl, vinyl benzyl chloride, vinyl benzyl floride, vinyl benzyl bromide,3-phenylpropenyl chloride, ##STR6##

The thermoplastic polyarylene polyethers are rendered "cross-linkable"through the incorporation of unsaturated moieties This is accomplishedconveniently by replacing saturated agents, such as, methyl chloride, anend-capping reagent, with an unsatuxated reagent. The resulting resinscontain unsaturated group at the chain ends. The composition iscross-linkable in the presence of a suitable free radical initiator.Upon curing these end-capped polysulfone compositions have been shown toprovide improved stress-cracking resistance and better adhesiveproperties. They are also useful for various polymer modificationpurposes particularly as a "rigid block" in forming block and graftcopolymers.

The end-capping reaction, i.e., reaction step (3), is carried out byreacting the monovalent unsubstituted organo compound with the alkalimetal phenoxide-capped polyarylene polyether resin produced by reactionstep (2). The stoichiometric proportions are two moles of unsubstitutedorgano compound per mole of polyarylene polyether resin. It is preferredto employ about a 2 to 10 mole percent stoichiometric excess of theunsubstituted organo compound. The reaction mixture preferably should besubstantially anhydrous. The reaction medium can be the same solventsystem that was employed for reaction steps (1) and (2). The reaction iscarried out at elevated temperatures, e.g., at from about 110° C. toabout 165° C. At the recommended temperature range, the reaction willusually take from about 10 to about 90 minutes. The completion of thereaction can be detected by treating a sample of the reaction mixturewith bromocresol purple indicator. When the alkali metal phenoxide hasreacted, the treated sample will be greenish yellow in color.

At the completion of the reaction, the reaction mixture can be cooled,filtered to remove salt by-product, and then the end-capped polyarylenepolyether resin can be recovered by coagulation in a non-solvent for theresin, e.g., methanol or isopropyl alcohol. Preferably the reactionmixture and the resin is kept anhydrous until the resin has beenrecovered as a solid.

The substantially equimolar one-step reaction of a double alkali metalsalt of a dihydric phenol with a dihalobenzenoid compound is done in thepresence, for example, of specific liquid organic sulfoxide or sulfonesolvents under substantially anhydrous conditions. Catalysts are notnecessary for this reaction. Another feature of the invention involvessimultaneously contacting substantially equimolar amounts of an alkalimetal double salt of a dihydric phenol and a dihalobenzenoid compoundwith a solvent mixture comprising an azeotrope former and a sulfoxide orsulfone reaction solvent in a weight ratio of from about 10:1 to about1:1, preferably from about 4:1 to about 3:1, removing water from thereaction mass as an azeotrope with the azeotrope former untilsubstantially anhydrous conditions are attained, adjusting the ratio ofazeotrope former to reaction solvent from about 1:1 to about 1:10,preferably from about 1:3 to about 1:4, by removing excess azeotropeformer, and reacting the alkali metal double salt with thedihalobenzenoid compound in the liquid phase of the sulfoxide or sulfonereaction solvent.

The useful sulfoxide or sulfone solvents are those of the formula:

    R--S(O).sub.v --R

wherein each R represents a monovalent lower hydrocarbon group free ofaliphatic unsaturation of the alpha carbon atom, and preferably containsless than about 8 carbon atoms or when connected together represents adivalent alkylene group with v being an integer from 1 to 2 inclusive.Thus, in all of these solvents all oxygens and two carbon atoms arebonded directly to the sulfur atom. Thus, contemplated for use in theinvention are such solvents as those having the formula: ##STR7##wherein the R groups are lower alkyl, such as methyl, ethyl, propyl,butyl and like groups and aryl groups such as phenyl and alkyl phenylgroups as well as those where the R groups are interconnected as in adivalent alkylene bridge, such as: ##STR8## as in thiophene oxides anddioxides. Specifically mentionable of these solvents but by no meansexhaustive of these solvents are dimethylsulfoxide, dimethylsulfone,diethylsulfoxide, diethylsulfone, diisopropylsulfone,tetrahydrothiophene 1,1-dioxide (commonly called tetramethylene sulfoneor sulfolane) and tetrahydrothiophene-1 monooxide. The dimethylsulfoxidehas been found to be the most useful as the solvent for this reactionbecause it is a solvent for the widest variety of reactants as well asfor the resulting polymer of the reaction. Aliphatic unsaturation on thealpha-carbon atom, such as occurs in divinyl sulfone and sulfoxide,should not be present as such materials tend to be reactive andpolymerize under the conditions of this reaction. However, unsaturationon a beta-carbon atom or one further removed from the sulfur atom can betolerated and such solvents can be employed in this reaction.

In situations where it is desired to prepare the alkali metal salt ofthe dihydric phenol in situ in the reaction solvent, the dihydric phenoland an alkali metal hydroxide are admixed in essentially stoichiometricamounts and normal precautions taken to remove all the water ofneutralization preferably by distillation of a water-containingazeotrope from the solvent-metal salt mixture. It has been convenient toemploy benzene, xylene, halogenated benzenes or other inert organicazeotrope-forming organic liquids in performing this. Heating the alkalimetal hydroxide, dihydric phenol and small amounts of the azeotropeformer to reflux for several hours while removing the azeotrope is themost desirable. However, it is obvious that any other technique forremoving essentially all of the water can be equally satisfactory.

It is not essential and critical in this reaction that all of theazeotropic former be removed before the reaction of the alkali metalsalt of the bisphenol with the dihalobenzenoid compound. In fact, it isdesirable in some instances to employ an amount of such material inexcess of that needed to azeotrope off all of the water, with thebalance being used as a co-solvent or inert diluent with the sulfone orsulfoxide principal solvent. Thus, for instance, benzene, heptane,xylene, toluene, chlorobenzene, dichlorobenzene or like inert liquidscan be beneficially employed.

The azeotrope former can be one either miscible or immiscible with thesulfone or sulfoxide major solvent. If it is not miscible it should beone which will not cause precipitation of the polymer in the reactionmass. Heptane is such a solvent. When employed, it will merely remaininert and immiscible in the reaction mass. If the azeotrope former wouldcause precipitation of the polymer, it should be removed almostcompletely from the reaction mass before initiating polymerization. Forsuch reasons, it is preferred to employ azeotrope formers which aremiscible with the major solvents and which also act as co-solvents forpolymer during polymerization. Chlorobenzene, dichlorobenzene and xyleneare azeotrope formers of this class. Preferably the azeotrope formershould be one boiling below the decomposition temperature of the majorsolvent and be perfectly stable and inert in the process, particularlyinert to the alkali metal hydroxide when the alkali metal salt of thedihydric phenol is prepared in situ in the presence of the inert diluentor azeotrope former. It has been found that chlorobenzene ando-dichlorobenzene serve particularly well as the inert diluent and areable to significantly reduce the amount of the sulfone or sulfoxidesolvent necessary. The co-solvent mixture using even as much as 50percent of the halogenated benzene with dimethylsulfoxide, for example,not only permits the formed polymer to remain in solution and thusproduce high molecular weight polymers, but also provides a veryeconomical processing system, and an effective dehydration operation.

Any of the alkali metal hydroxides can be employed in this technique,that is to say any alkali metal salt of the dihydric phenol can be usedas the one reactant. Potassium and cesium salts have been found to reactconsiderably faster than the sodium salts, but due to expense of thecesium salts, the potassium salts are preferred. As heretoforeindicated, the alkali metal salt should, of course, be the double metalsalt, i.e., both aromatic hydroxyl groups being saponified, in order toprepare these products. Single metal salts ordinarily limit themolecular weight of the product. While this may be desirable as a chainterminator or molecular weight regulator near the terminus of thereaction period, the initial reaction and the major portion thereofshould be with the double alkali metal salt of the dihydric phenol. Thealkali metal moieties of this compound however can be the same ordifferent alkali metals.

Substantially equimolar amounts of the alkali metal double salt of adihydric phenol (or a dihydric phenol for in situ conversion to thesalt) and a dihalobenzenoid compound are simultaneously contacted with asolvent mixture comprising an azeotrope former and a sulfoxide orsulfone reaction solvent in a ratio of from about 10:1 to about 1:1 byweight based on the combined weight of the azeotrope former and reactionsolvent. When water is present in this solvent mixture, a phaseseparation occurs even between normally miscible liquids creating twoliquid phases. When this phase separation occurs, the water and hydratedalkali metal double salt of a dihydric phenol are preferentiallydissolved in the sulfoxide or sulfone reaction solvent phase and thedihalobenzenoid compound is preferentially dissolved in the azeotropeformer phase. The initial ratio of azeotrope former to reaction solventis critical in this respect because with lesser amounts of azeotropeformer, two liquid phases are not formed and undesirable hydrolysis ofthe dihalobenzenoid compound occurs. Only when the ratios specified areused does a phase separation occur which isolates the dihalobenzenoidcompound from hydrolysis by the water in the system.

If dry crystalline alkali metal salt of a dihydric phenol is employed,problems relative to obtaining anhydrous conditions are essentiallyavoided. However, drying the salt and keeping it dry during transfer andcharging is difficult. It is more advantageous to employ a hydratedalkali metal salt which is dehydrated in the reaction mass by removingthe water of hydration. Water then can be present or formed in thereaction mass as the water of hydration of a hydrated alkali metal salt,as the water of neutralization formed during the in situ conversion of adihydric phenol to the alkali metal double salt, or as water present ineither the azeotrope former or the reaction solvent. During the in situconversion, the hydrated salt is formed first which is then dehydratedupon the removal of water.

When the two liquid phases are formed, it is important that the water inthe system be removed as quickly as possible, usually by refluxing themixture at about the boiling point of the azeotrope former untilsubstantially all of the water is removed. During the water removal, thedehydrated alkali metal double salt, which is insoluble in the reactionsolvent at the reflux temperatures, precipitates. The fact that all thewater has been removed is usually signaled by no further precipitateformation, no further azeotrope formation, and the formation of oneliquid phase when miscible liquids are used. After the water has beenremoved, excess azeotrope former is removed by distillation until theratio of azeotrope former to sulfoxide or sulfone reaction solvent isabout 1:1 to 1:10. Only when the amount of azeotrope former is reducedto within these ratios, does significant polymerization occur.

The residuum of the dihydric phenol of these alkali metal salts is notnarrowly critical. It can be, for instance, a mononuclear phenylenegroup as results from hydroquinone and resorcinol, or it may be a di- orpolynuclear residuum. Likewise the residuum be substituted with otherinert nuclear substituents such as halogen, alkyl, alkoxy and like inertsubstituents.

From a practical standpoint, limitations on polymer molecular weightscan be expected when the dihydric phenol or the alkali metal derivativethereof contain strong electron withdrawing groups. This may result inlower molecular weight polymers or impractically slow reaction rates.Hence, the dihydric phenol should be a weakly acidic dinuclear phenol,such as, the dihydroxy diphenyl alkanes or the nuclear halogenatedderivatives thereof, such as, the 2,2- bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)2-phenyl ethane, bis(4-hydroxyphenyl)methane, orthe chlorinated derivatives containing one or two chlorines on eacharomatic ring. While these halogenated bisphenolic alkanes are moreacidic than the non-halogenated bisphenols and hence slower inreactivity in this process, they do impart valuable flame resistance tothese polymers. Other materials also termed appropriately "bisphenols"are also highly valuable and preferred. These materials are thebisphenols of a symmetrical or unsymmetrical joining group, as, forexample, ether oxygen (--O--), ##STR9## or hydrocarbon residue in whichthe two phenolic nuclei are joined to the same or different carbon atomsof the residue such as, for example, the bisphenol of acetophenone, thebisphenol of benzophenone, the bisphenol of vinyl cyclohexene, thebisphenol of alpha-pinene, and the like bisphenols where thehydroxyphenyl groups are bound to the same or different carbon atoms ofan organic linking group.

Such dinuclear phenols can be characterized as having the structure:##STR10## wherein Ar is an aromatic group and preferably is a phenylenegroup, Y and Y₁ can be the same or different inert substituent groups asalkyl groups having from 1 to 4 carbon atoms, halogen atoms, i.e.,fluorine, chlorine, bromine or iodine, or alkoxy radicals having from 1to 4 carbon atoms, m and z are integers having a value from 0 to 4,inclusive, and R is representative of a bond between aromatic carbonatoms as in dihydroxydiphenyl, or is a divalent radical, including forexample, inorganic radicals as ##STR11## --O--, --S--, --S--S--, --SO₂--, and divalent organic hydrocarbon radicals such as alkylene,alkylidene, cycloaliphatic, or the halogen, alkyl, aryl or likesubstituted alkylene, alkylidene and cycloaliphatic radicals as well asalkalicyclic, alkarylene and aromatic radicals and a ring fused to bothAr groups.

Examples of specific substituted dihydric polynuclear phenols includeamong others: the substituted bis-(hydroxylphenyl)alkanes, such as,2,2-bis-(4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenyl methane,bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane,bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane,1,1-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxy-2-chlorphenyl)ethane,1,1-bis-(3-methyl-4-hydroxyphenyl)propane,1,3-bis-(3-methyl-4-hydroxyphenyl)propane,2,2-bis-(3-phenyl-4-hydroxyphenyl)propane,2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis-(2-isopropyl-4-hydroxyphenyl)propane,2,2-bis(4-hydroxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pentane,3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heptane,bis-(4-hydroxyphenyl)phenylmethane,2,2-bis-(4-hydroxyphenyl)-1-phenylpropane,2,2-bis-(4-hydroxyphenyl)1,1,1,3,3,3,hexafluoropropane and the like; thesubstituted di(hydroxyphenyl)sulfones, such as,bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone,5'-chloro-2,4'-dihydroxydiphenyl sulfone,5'-chloro-4,4'-dihydroxydiphenyl sulfone and the like; and thesubstituted di(hydroxyphenyl)ethers, such as,bis-(4-hydroxyphenyl)ether, the 4,3'-, 4,2'-, 2,2'- and2,3'-dihydroxydiphenyl ethers, 4,4'-dihydroxy-2,6-dimethyldiphenylether, bis-(4-hydroxy-3-isobutylphenyl)ether,bis-(4-hydroxy-3-isopropylphenyl)ether,bis-(4-hydroxy-3-chlorophenyl)ether,bis-(4-hydroxy-3-fluorophenyl)ether, bis-(4-hydroxy-3-bromophenyl)ether,bis-(4-hydroxynaphthyl)ether, bis-(4-hydroxy 3-chloronapthyl)ether,4,4'-dihydroxyl-3,6-dimethyoxydiphenyl ether,4,4'-dihydroxy-2,5-diethoxydiphenyl ether and the like.

In the invention a mixture of two or more different dihydric phenols canbe used. Thus, herein the --E-- or --E'-- residuum in the polymerstructure can actually be the same or different aromatic residue. Asherein used the term E or E' when defined as being the "residuum of thedihydric phenol" of course refers to the residue of the dihydric phenolafter the removal of the two aromatic hydroxyl groups. Thus as isreadily seen these polyarylene polyethers contain recurrding groups ofthe residuum of the dihydric phenol and the residuum of the benzenoidcompound bonded through aromatic ether oxygen atoms.

Any dihalobenzenoid compound or mixture of dihalobenzenoid compounds canbe employed in the invention which compound or compounds has the twohalogens bonded to benzene rings having an electron withdrawing group inat least one of the positions ortho and para to the halogen group. Thedihalobenzenoid compound can be either mononuclear where the halogensare attached to the same benzenoid ring or poly nuclear where they areattached to different benzenoid rings, as long as there is an activatingelectron withdrawing group in the ortho or para position of thatbenzenoid nucleus. Any of the halogens may be the reactive halogensubstituents on the benzenoid compounds. Fluorine and chlorinesubstituted benzenoid reactants are preferred; the fluorine compoundsfor fast reactivity and the chlorine compounds for theirinexpensiveness. Fluorine substituted benzenoid compounds are mostpreferred, particularly when there is a trace of water present in thepolymerization reaction system. However, this water content should bemaintained below about 1 percent and preferably below 0.5 percent forbest results.

Any electron withdrawing group can be employed as the activator group inthese compounds. It should be, of course, inert to the reaction, butotherwise its structure is not critical. Preferred are the strongactivating groups such as the sulfone group ##STR12## bonding twohalogen substituted benzenoid nuclei as in the 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenyl sulfone, although such other strongwithdrawing groups can also be used. The more powerful of the electronwithdrawing groups give the fastest reactions and hence are preferred.It is further preferred that the ring contain no electron supplyinggroups on the same benzenoid nucleus as the halogen; however, thepresence of other groups on the nucleus or in the residuum of thecompound can be tolerated. Preferably, all of the substituents on thebenzenoid nucleus are either hydrogen (zero electron withdrawing), orother groups having a positive sigma value [as set forth in J. F.Bunnett, Chem. Rev. 49,273 (1951), and Quart. Rev., 12, 1 (1958)]. Theelectron withdrawing group of the dihalobenzenoid compound can functioneither through the resonance of the aromatic ring, as indicated by thosegroups having a high sigma value, i.e., above about +0.7, or byinduction as in perfluoro compounds and like electron sinks. Preferablythe activating group should have a high sigma value, preferably above1.0, although sufficient activity to promote the reaction is evidence inthose groups having a sigma value above 0.7, although the reaction ratewith such a low powered electron withdrawing group may be somewhat low.

The activating group can be basically either of two types:

(a) monovalent groups that activate one or more halogens on the samering as a nitro group, phenylsulfone, or alkylsulfone, cyano,trifluoromethyl, nitroso, and hetero nitrogen as in pyridine; or

(b) divalent group which can activate displacement of halogens on twodifferent rings, such as the sulfone group ##STR13## the carbonyl group##STR14## the vinyl group ##STR15## the sulfoxide group ##STR16## theazo-group --N═N; the saturated fluorocarbon groups --CF₂ CF₂ --; organicphosphine oxides ##STR17## wherein R is a hydrocarbon group, and theethylidene group ##STR18## where X can be hydrogen or halogen or whichcan activate halogens on the same ring such as withdifluorobenzoquinone, 1,4- or 1,5- or 1,8-difluoroanthraquinone.

A plurality of electron withdrawing groups can be employed if desired,including electron withdrawing groups having a sigma value below about+0.7, provided the cumulative sigma influence on each of the reactivehalogen groups of the halobenzenoid compound is at least about +0.7. Ifdesired, the polymers may be made with mixtures of two or moredihalobenzenoid compounds each of which has this structure, and whichmay have different electron withdrawing groups.

As used herein, the term E or E' when defined as being the "residuum ofthe benzenoid compound" refers to the aromatic or benzenoid residue ofthe compound after the removal of the halogen atoms on the benzenoidnucleus.

Dimethylsulfoxide decomposes at its boiling point, i.e., about 189° C.;it is desirable to keep the reaction temperature below this to avoidsuch problems when employing this solvent.

The reaction temperature can be effectively increased even above thenormal boiling point of the solvent or mixture of solvents by the use ofpressure in the system. However, for most practical reactionscontemplated herein, atmospheric pressures are quite adequate, though ifdesired pressures as high as 1000 psig or more can be employed.

The molecular weight of the polymer can be easily controlled in thisprocess by the addition of a precipitating solvent to the reactionmixture when the desired reduced viscosity of the resin is secured orwhen the indicated viscosity of the polymerization mass is high enoughto indicate the desired molecular weights are achieved. It is alsopossible to terminate the growing polymer chain by the addition of amonofunctional chain stopper, such as an alkyl halide or other suitablecoreactant.

The molecular weight of the end-capped resins is indicated by reducedviscosity in indicated solvents. The viscosity of a resin solution bearsa direct relationship to the weight average molecular size of the resinchains, and can be used to characterize the degree of polymerization.The reduced viscosity values used herein are of significance onlyrelative to each other rather than in any absolute sense, and for thisreason other polyether-solvent systems can be employed as an indicationof the relative molecular weight of these resins. When solvents otherthan chloroform are employed, the required average molecular sizerelationship can readily be established by reference to the reducedviscosity values defined herein even though the numerical reducedviscosity values of the alternative system may be different.

In the in situ process (conversion) the preferred solvent isdimethylacetamide; the process uses K₂ CO₃.

The preferred class of end-capped thermosetting resins of the inventionare those polysulfone where the thermosetting polyarylene polyetherresin is composed of recurring units having the formula: ##STR19##wherein R is hydrogen, lower alkyl, lower aryl and halogen substitutedlower alkyl and lower aryl groups. Most preferably R is methyl. Thelower alkyl groups have from 1 to 4 carbon atoms.

As used herein, the polysulfone-vinyl reactive resins or PSF-VR are theabove end-capped resins when R is methyl and the end-capping moietiesare alkylene, aralkylene or cycloalkylene moieties.

Also as used herein, the (prior art) polysulfone-silane reactive resinsor PSF-SR refer to silane end-capped polyarylene polyether polymers madefrom bisphenol-A and dihalodiphenylsulfone. (See U.S. Pat. No. 4,093,600and 4,183,874.)

Because of their thermoset nature, the cured polysulfonevinyl reactiveresins exhibit a markedly improved environmental stress-crack resistanceand a better dimensional stability at elevated temperatures than thoseof the thermoplastic polysulfone.

The polysulfone-vinyl reactive resin is prepared by a two step process,namely, polymerization followed by end-capping. In the polymerizationstep, bisphenol A and dihalodiphenylsulfone are polymerized in thepresence of an alkali metal hydroxide, an alkali metal oxide and/orammonium hydroxide. A deficient amount of sulfone monomer is used duringthe polymerization to produce the desired sodium phenate terminatedoligomers. By varying the sulfone monomer/bisphenol A charge ratio,polysulfone-vinyl reactive resin of a wide range of molecular weightscan be prepared.

The sequence of reactions of the preparation process of the invention isrepresented schematically below wherein the end-capping reagent is vinylbenzyl chloride: ##STR20##

In the polymerization step, the preferred alkali metal hydroxide issodium hydroxide. Useful alkali metal hydroxides include lithiumhydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.Useful alkali metal oxides include sodium oxide, lithium oxide,potassium oxide, rubidium oxide and cesium hydroxide. Ammonium hydroxideis also useful in the polymerization step in place of the sodiumhydroxide.

The polymerization step is carried out at a temperature preferablybetween 163° and 165° C. in a mixed solvent composed of dimethylsulfoxide (DMSO) and monochlorobenzene (MCB), although any othersuitable solvent(s) such as dimethyl acetamide (DMAC) can also beemployed. Any suitable polymerization temperature (e.g., 120° to 185°C.) can be used. Precautions which are normally observed during thepreparation of standard polysulfone are equally important here toachieve quality products. Of particular importance is the caustic chargewhich affects both the "color" and "stability" of the finishedpolysulfone-vinyl reactive resin in addition to its anticipated effecton the molecular weight and composition of the latter.

Useful polar solvents include: alcohols, such as, methanol, ethanol,n-propyl alcohol, n-butyl alcohol, amyl alcohol, isopropyl alcohol,sec-butyl alcohol, isobutyl alcohol and 4-methyl 2-pentanol; ethers,such as ethyl ether, diethyl Cellosolve and butyl ether; aldehydes, suchas, benzaldehyde and furfural; triethyl phosphate; and amides, such as,N,N-dimethyl formamide, acetamide and butramide.

In the end-capping or terminating step, the alkali oxy (e.g., NaO--) endgroups of the polysulfone are reacted with a halo organo compoundcontaining a terminal or near terminal unsaturated group.

The compounds used for end-capping or terminating are halogenated,unsaturated compounds. The end-capping reagents are described by thegeneric formula:

    XZ

wherein X is a halogen, preferably chlorine, and Z is an unsaturatedorganic radical. More specifically, Z is usually a reactive, unsaturatedradical having an alkylene, aralkylene or cycloalkylene moiety (linkedto the halogen). Most halophenyl compounds have limited reactivity.

Examples of the preferred end-capping reagents are allyl chloride,2-chloroethylacrylate, 2-chloroethylmethacrylate,chloromethyldimethylvinylsilane, vinyl benzyl chloride and 2-chloroethylvinyl ether.

The halo organo compound reacts like an alkyl halogen with the alkalioxy end groups. Although end-capping is preferably done at a temperatureof 115° to 120° C., no deleterious effect was usually evident even whenthe end-capping was performed at the preferred polymerizationtemperature which is from 163° to 165° C. Because of a much greaterreaction rate at the latter temperature, the required reaction time isshortened drastically. Apparently a more complete reaction also resultsat the high temperature levels due to lower viscosities. Any suitabletemperature can be used in the end-capping step.

Preferably anhydrous condition during the end-capping stage, coupledwith a reasonably good hydrolytic stability of the halo organo compound,is used whereby premature gelation of the polysulfone-vinyl reactiveresin is normally not a problem in the reactor. Upon completion of theend-capping step, the reaction mixture should be neutral which can bereadily diluted with dry monochlorobenzene (or other suitable solvent)and filtered without difficulty. However, the presence of residualalkalinity, which may result from either a deficiency in end-cappingreagent charged or an incompletion in reaction, can cause problemsduring subsequent filtering when the polymer solution is exposed toeither atmospheric moisture and/or wet diluent. For this reason a speedyproduct recovery is recommended whenever the above circumstance ispresent or suspected.

The preferred (average) molecular weight of the polysulfone-vinylreactive resin is between 5,000 and 15,000, although higher and lowermolecular weights are within the scope of the invention. Thepolysulfone-vinyl reactive resin can range in size from oligomer topolymer. The average molecular weight of the polysulfone-vinyl reactiveresin can be determined by the NMR technique.

The polysulfone-vinyl reactive resin can be separated or recovered fromthe reaction mixture by any appropriate method, but the coagulationmethod and the melt recovery process are preferred Recovery bycoagulation is normally done in isopropanol (or methanol). The meltrecovery production process involves removing the solvents by passingthe polymer solution through a recovery system consisting of aconcentrator, a devolatilizer and a Marshall mill.

While polysulfone-silane reactive resins are outside of the scope of theinvention, they are frequently used herein for comparitive purposes. Thepolysulfone-silane reactive resins are structurally very similar to thepolysulfone-vinyl reactive resins of the invention, except for theend-capping by reaction with silane groups such as3-chloropropyltrimethoxysilane. The production process is very similarfor the two types of end-capped polysulfones. The polysulfone-silanereactive resins have been prepared in a broad range of molecular weightsby varying the monomer feed ratio in the synthesis of the oligomers. Thepolysulfone-silane reactive resins have excellent hydrolytic stabilityin bulk form below their glass transition temperature. They can even besuspended in water without premature gelation. Cross-linking occursreadily above the glass transition temperature, and the cure rate can befurther increased by prehydrolysis of the silylalkoxy end groups or bythe use of catalysts. Cross-linked polysulfone-silane reactive resinshave mechanical and electrical properties comparable to those ofstandard polysulfone. Cured polysulfone-silane reactive may enablehigher use temperature limits than thermoplastic polysulfone resins, andlarge improvements over such thermoplastic polysulfone resins are foundin their solvent resistance (environmental stress crack resistance).Also, due to the silane end groups, a built-in bonding capability existstowards many inorganic and metallic surfaces

Concerning the polysulfone-vinyl resins in Table IV below, there was notany evidence of thermally initiated polymerization of the reactive endgroups during the end-capping step. Preferably, however, the reactiontemperature is kept below 125° C. during the end-capping step and thesystem is kept under positive nitrogen pressure throughout.

Due to the absence of moisture sensitive end groups, thepolysulfone-vinyl reactive resins are usually easier to handle thanpolysulfone-silane reactive resins during preparation. Once theend-capping reaction is complete, the polysulfone-vinyl reactive resinsmay be exposed to water or wet solvent without being affected. The onlyexceptions, however, are the polysulfone-vinyl reactive resins havingmethacryloxy or acryloxy end groups which are hydrolized readily bymoisture. For this reason, the chloroalkyl esters of such are preferred.

Unlike the polysulfone-silane reactive resin which has three reactivesites for each end-group, the end-groups of all of the polysulfone-vinylreactive resins shown in Table I are monofunctional. This differencerequires that a precise stoichiometry of the reactants be maintained inorder to produce the desire curable product, that is, a completelyend-capped resin. When there is either an excess amount of bisphenol Aor a deficiency in caustic charge (NaOH), a lower end-capping efficiencywill result.

When 2-chloroethyl methacrylate (acrylate) is employed, the occurrenceof dehydrochlorination during the end-capping step becomes apossibility. An excess amount of end-capping reagent is usually added tooff-set any potential loss due to side reactions.

The molecular weights of the polysulfone-vinyl reactive resins arecontrolled by adjusting the stoichiometry cf mononers in the feed. Usingreduced viscosity (R.V.) as a measure of the molecular weight, thesulfone bisphenol-A molar ratios used in the feed are plotted againstthe deduced viscosity values of a series of vinyl benzyloxy end-cappingpolysulfone-vinyl reactive resins in FIG. 3. The other polysulfone-vinylreactive resins (not shown in FIG. 3) follow roughly the samerelationship.

Polysulfone-vinyl reactive resins are compositionally identical to thepolysulfone-silane reactive resins except the end-groups. Consequently,the physical properties of the two types of resins are quite similareven though they cure by two distinctively different mechanisms. Acomparison of the properties of these two resins is illustrated in TableI below.

                  TABLE I                                                         ______________________________________                                        A COMPARISON BETWEEN PSF-VR.sup. (a)                                          AND PSF-SR.sup. (b) RESINS                                                    Property PSF-VR.sup. (a)     PSF-SR.sup. (b)                                  ______________________________________                                        Appearance                                                                             White Fluff         Same                                             Solubility                                                                             Soluble in chlorinated hydro-                                                                     Same                                                      carbons, THF, Dioxane, DMSO,                                                  DMF, etc.                                                            Tg (uncured)                                                                           Increases with increasing --Mn                                                                    Same                                             Tg (cured)                                                                             Equivalent to that of standard                                                                    Same                                                      polysulfone                                                          Thermal  Will advance gradually above                                                                      Same                                             Stability                                                                              Tg.sup.(c)                                                           Hydrolytic                                                                             Good either in bulk or in                                                                         Good in bulk                                     Stability                                                                              solution                                                             Curing   Addition Polymerization                                                                           Condensation                                     Reaction                     Polymerization                                   Curing   Peroxide, radiation (UV                                                                           Heat and                                         Method   Electron Beam, etc.)                                                                              moisture                                         By-product                                                                             None.sup.(d)        Methanol and                                     evolved                      water                                            during                                                                        Adhesive None                Excellent                                        Capability                                                                    ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl reactive.                                           .sup.(b) Polysulfonesilane reactive.                                          .sup.(c) Depending on the reactivity of the end groups.                       .sup.(d) Not counting the decomposition products from the peroxide if         used.                                                                    

The thermal stability of the polysulfone-vinyl reactive resinsapparently is much influenced by the nature of the end groups. Resinsend-capped with the methacryloxy ethoxy groups were found to retaintheir thermoplasticity upon repeated thermal abuses at elevatedtemperatures, while those having the vinyl benzyloxy end groups wouldadvance under similar conditions. This difference in behavior isconsistent in the fact that, while the methacrylates are known to befairly stable (thermally) in the absence of an initiator, the styrenemonomers will undergo thermal-initiated polymerization--see W. R.Sorenson and T. W. Campbell, "Preparative Methods of Polymer Chemistry",2nd Edition, Interscience (1968), pp. 210 and 253.

The polysulfone-vinyl reactive resins are not subject to hydrolysisunder normal conditions. They are therefore more tolerant of water oralkaline contaminates than the polysulfone-silane reactive resins.

The polysulfone-vinyl reactive resins share the common unique featurewith the polysulfone-silane reactive resins in exhibiting excellentstability at ambient temperatures. This phenomenon has been attributedto the high glass transition temperature of the polysulfone backbonewhich severely restrictsthe mobility of the end groups. Curing of thepolysulfone-vinyl reactive resins is effected, however, by heating abovethe glass transition temperature of polysulfone, usually in the presenceof a free radical initiator.

The preferred free radical initiators are the peroxides, and thepreferred peroxide is dicumyl peroxide. Examples of useful peroxides arethe dialkyl peroxides, such as, di-t-butyl peroxide, lauroyl peroxide,decanoyl peroxide, 2-methylpentanoyl peroxide, acetyl peroxide,2,5-dimethyl-2,5-di (t-butylperoxy-hexane and2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, the diaryl peroxides, suchas, benzoyl peroxide, the alkaryl peroxides, such as, dicumyl peroxide,the sulfonyl peroxides, such as acetyl cyclohexysulfonyl peroxide andacetyl sec-heptylsulfonyl peroxide, the peresters, such as, t-butylperbenzoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate,1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate,2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxymaleicacid, 00-t-butyl 0-isopropyl monoperoxycarbonate,2,5-dimethyl-2,5-bis-(benzoylperoxy)hexane, t-butyl peracetate anddi-t-butyl diperoxyphthalate, the peroxydicarbonates, such as,di(isopropyl) peroxydicarbonate, diisopropyl peroxydicarbonate,di(secbutyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate,dicyclohexyl peroxydicarbonate and dibenyl peroxydicarbonate. Theorganometallic peroxides, such as, vinyl tris(t-butyl peroxy)silane, thehydroperoxides, such as, t-butyl hydroperoxide and cumyl hydroperoxide,1,1,3,3-tetramethylbutyl hydroperoxide and2,5-dihydroperoxy-2,5-dimethylhexane, the azo compounds, such as,2,2'-azobis(isobutyronitrile) and2,2'-azobis(2,4-dimethylvaleronitrile).

The reactivity of a polysulfone-vinyl reactive resin will vary greatly,depending on the type of end groups employed. Those having alloxy orvinyl ether ethoxy end groups react with difficulty, those terminatedwith either methacryloxy ethoxy or acryloxy ethoxy end groups arereactive but the presence of an initiator is usually necessary, andthose with vinyl benzyloxy end groups will react upon thermal initation.

A neat (pure) polysulfone-vinyl reactive resin, even with the reactivevinyl benzyloxy and groups, requires prolonged heating at temperaturesabove the glass transitional temperature of polysulfone to reach a highdegree of cross-linking. The cure rate can be accelerated by theaddition of a peroxide. This approach, however, is often hampered by thelack of a suitable peroxide which will endure the high processtemperature necessary for these resins. At ambient temperatures, a neatpolysulfone-vinyl reactive resin is not curable by either electron beamor U. V. radiation due to a restricted molecular mobility.

An important finding in the curing behavior of the polysulfone-vinylreactive (PSF-VR) resins is that they are soluble in styrene monomerover the entire compositional range, and that the resultantpolymer/comonomer binder system will polymerize and yield a truecopolymer. The latter may be either a thermoset or thermoplasticdepending on the polysulfone-vinyl reactive/styrene feed ratio, and themethod of polymerization. Bulk polymerization usually leads tocross-linked products while solution polymerization at lowpolysulfone-vinyl reactive concentrations often produces solublecopolymers. A polysulfone-vinyl reactive resin/styrene binder system isnot only peroxide curable, it also can be cured by exposure to electronbeahm or U. V. radiation in the presence of a photo-sensitizer. In thelatter cases, styrene also acts as a diluent for the polysulfone-vinylreactive resin to provide the necessary mobility at ambienttemperatures.

In addition to styrene, polysulfone-vinyl reactive resins can be mixedand cured with a variety of other comonomers to produce copolymershaving a broad range of thermal and mechanical properties. This approachnot only permits the use of polysulfone-vinyl reactive resins forvarious polymer modification purposes but also provides an attractivemay of reducing the cost of the resin through compounding with cheapercomonomers. Through the selection of comonomers and their loadings, itis often feasible to tailor-make formulations to fulfill thecost/performance requirements of different end-uses. Commercialcomonomers which are suited for the above purpose include styrene,α-methyl styrene, divinyl benzene, acrylates, methacrylates,acrylonitrile, dialkylphthalates, trimethylolpropanetrimethacrylate,triallylcyanurate, α-methacryloylpropyltrimethoxysilane and diacetoneacrylamide. By employing polysulfone-vinyl reactive resins of variousinitial molecular weights, polysulfone-vinyl reactive resin/comonomerbinder systems having different cross-linking densities as well aspolysulfone block lengths can be prepared.

The use of a comonomer in conjunction with the polysulfone-vinylreactive resin offers a number of advantages: (a) the formulation isrendered curable b conventional methods; (b) property modifications arepermitted through a wide selection of comonomers; and (c) flexibility isallowed in meeting the cost/performance requirements for differentend-use areas. Upon cross-linking, polysulfone-vinyl reactive resinsexhibit a marked improvement in environmental stress-crack resistanceover the regular polysulfone, similar to that of the polysulfone-silanereactive resins. The degree of improvement is usually parallel to theincrease in cross-linking density of the cured material.

Because of the dual functionalities present in each polysulfone-vinylreactive molecule, polymerization usually leads to the formation of anetwork structure. However, under certain circumstances thepolysulfone-vinyl reactive chains can be extended with another comonomerwhile retaining its thermoplasticity. These thermoplastic resins can becompression-molded to clear or slightly hazy plaques; they are usuallybrittle and resemble polystyrene.

Polysulfone has exceptional chemical resistance, particularly in astrong alkaline environment. This quality makes the polysulfone-vinylreactive resin a suitable matrix resin for fabricatingcorrosion-resistant composite materials. Polysulfone-vinyl reactiveresins, while retaining most of the polysulfone's properties, exhibit anumber of additional features which are highly desirable for the coatingapplications. Because of their oligomeric nature, they are characterizedby high solubilities in polysulfone-soluble solvents, low melting pointsand good melt flow characteristics which make them suitable for avariety of fabrication processes, particularly the solution and powercoating techniques. The reactive end-groups of the polysulfone-vinylreactive resins permit curing by either heat, peroxide, U.V.,electon-beam radiation or other suitable energy sources. Once cured, thecoating is transformed to a clear, rigid, tough thermoset possessingexcellent solvent, chemical and thermal resistance. In contrast to thesilane end-capped counterparts, polysulfone-vinyl reactive resins lackinherent bonding capabilities. Better adhesion, however, can be achievedby modifying with say unsaturated silane or silyl peroxide adhesionpromoters or suitable polar comonomers. The polysulfone-vinyl reactiveresins can be for a variety of coating applications including magnetwire coatings, photocurable coatings and and powder coatings.

Due to their reactive end-groups, polysulfone-vinyl reactive resins canbe modified to acquire improved properties over the parent polysulfone.This is exemplified by the broad spectrum of polysulfone-vinyl reactivecomonomer binder systems shown in Tables VI to X below. Thethermoplastic versions of the polysulfone-vinyl reactive resins areuseful, for instance, to bring out compatibility between polysulfone andinexpensive polystyrene.

The polysulfone-vinyl reactive resins are also useful as modifiers forother (reactive) polymers to impart certain desirable polysulfoneproperties. The resulting compositions can be either copolymers orinterpenetrating polymeric networks (IPN's). In addition, thepolysulfone-vinyl reactive resins can be used for formulatingphotocurable printing plates and for making membranes to take advantageof their mechanical rigidity, and chemical resistance; porosity in themembrane can be readily developed by solvent leaching upon curing.

The polysulfone-vinyl reactive/comonomer binder system of the inventionis often a cross-linked copolymer produced by chain extension with asuitable comonomer from the reactive end-groups of the polysulfone-vinylreactive resin. So the polysulfone-vinyl reactive/comonomer bindersystems should be handled like a thermoset. This behavior undoubtedlyrestricts its melt processability, but it also provides several usefulproperties being a thermoset. The broad spectrum of comonomers availableprovide a great deal of freedom to the formulation of such bindersystems. Styrene, acrylonitrile and divinyl benzene are among thepreferred comonomers for this purpose.

Vinylbenzylchloride is the preferred end-capping compound because of itscommercial ayailability, attractive economy and good reactivity. Adrawback of this reagent is that polysulfone-vinyl reactive resinshaving the vinyl benzyloxy end-groups are subject to thermal-initiatedpolymerization. This behavior complicates the melt recovery processemployed for the standard polysulfone as well as limits the operatingaltitude during melt fabrications. This difficulty can be resolvable bythe addition of a suitable inhibitor.

End-capping of 5,000 molecular weight, hydroxy terminated polysulfoneoligomer with vinylbenzyl chloride afforded a thermosetting compositionwith excellent solvent resistance. At 200 psi, this material did notrupture after twenty-five minutes of exposure of acetone, toluene, andtrichloroethylene. Although compression molded plaques were brittle thehigh cure speed and good flow behavior should make this material ofinterest in coating applications (e.g., powder coating).

The properties of the thermosetting polysulfone-vinyl reactive resin andtheir blends with some epoxy resins are listed in Table A below: The5,000 MW polysulfone-vinyl reactive resin/epoxy system exhibitedexcellent flow characteristics, solvent resistance, a high glasstransition temperature (Tg) and good tensile properties.

The environmental stress aging characteristics of vinylbenzyl chloridecapped polysulfone resins are listed in Table B below:

                  TABLE A                                                         ______________________________________                                                                          ELONGA-                                                           TENSILE     TION                                                      Tg,     STRENGTH,   @ BREAK,                                    COMPOSITE     °C.                                                                            PSI         %                                           ______________________________________                                        5,000 MW polysulfone-                                                                       160°                                                                           12,000      5                                           vinyl reactive resin/                                                         ERRE-0100                                                                     10,000 MW polysulfon-                                                                       166°                                                                           13,300      5                                           vinyl reactive resin/                                                         ERRE-0100                                                                     Vinylbenzylchloride                                                                         166°                                                                            3,040      1.2                                         capped 5,000 MW                                                               polysulfone-vinyl                                                             reactive resin                                                                Vinylbenzylchloride                                                                         --      11,000      6                                           Capped 10,000 MW                                                              polysulfone-vinyl                                                             reactive resin                                                                ______________________________________                                    

                                      TABLE B                                     __________________________________________________________________________    ENVIRONMENTAL STRESS AGING CHARACTERISTICS                                                TIME TO FAILURE                                                               STRESS      TRICHLORO-                                                        LEVEL                                                                              ACETONE                                                                              ETHYLENE                                                                              TOLUENE                                       __________________________________________________________________________    Vinylbenzylchloride                                                                       200 psi                                                                            >25 min.                                                                             >25 min.                                                                              >25 min.                                      Capped 5,000 MW PSF                                                           Vinylbenzylchloride                                                                       200 psi                                                                            inst.  480 sec.                                                                              inst.                                         Capped 10,000 MW PSF                                                          __________________________________________________________________________

The comonomer having at least one monovalent unsaturated organo radicalshould be one which is not gaseous at ambient conditions. Such comonomerpreferably also is compatible with the polysulfone-vinyl reactivemonomer. The term compatibility, as used herein, means that suchcomonomer has a reasonable degree of solubility in the polysulfone-vinylreactive. For example, styrene is completely soluble in thepolysulfone-vinyl reactive monomers, so styrene is very compatible withthe polysulfone vinyl reactive monomers. Acrylates have some solubilityin the polysulfone-vinyl reactive monomers, so acrylates have somecompatibility with the polysulfone-vinyl reactive monomers.Acrylonitriles also have a good degree of compatibility.

As used herein, the term "vinyl monomer" broadly means a monomercontaining at least one of the groups vinyl, vinylidene or vinylene.Vinyl is H₂ C═CH--; vinylidene is H₂ C═C═; and vinylene is --CH═CH--.Each of such terms includes substituted groups. (Broadly monomers havingat least one monovalent reactive unsaturated organo moiety are used asthe comonomers.)

Preferably the monovinyl monomer is a vinyl monomer having the formula:

    H.sub.2 C═CH--R

wherein R is a hydrogen atom, an alkyl group having from 1 to 4 carbonatoms, an alkoxy group having from 1 to 4 carbon atoms, an alkylcarboxylgroup having from 2 to 12, preferably from 2 to 10 carbon atoms, anitrile group, a halogen atom, preferably a chlorine atom, a phenylgroup, or an alkoxycarbonyl group having from 2 to 12, preferably from 2to 9 carbon atoms. A single vinyl monomer as well as mixtures of vinylmonomers can be used.

The compatible monovinyl monomers include: styrene; α-substitutedstyrenes, i.e. ##STR21## wherein R₂ is alkyl and/or alkoxy having 1 to 6carbon atoms; substituted styrene, i.e., R_(n) C₆ H_(5-n) CH═CH₂,wherein n is 1 to 5, R is chlorine, fluorine, bromine, iodine, alkylhaving 1 to 6 carbom atoms, alkoxy having 1 to 6 carbon, --CN or --NO₂ ;alkylacrylates wherein the alkyl has 1 to 11 carbons, preferably 1 to 6carbons; alkoxyacrylates, wherein the alkyl has 1 to 11 carbons,preferably 1 to 6 carbons; alkyl methacrylates, wherein the alkyl has 1to 10 carbons, preferably 1 to 6 carbons; alkoxy methacrylates, whereinthe alkyl has 1 to 10 carbons, preferably 1 to 6 carbons; allyl alkylethers, i.e., CH₂ ═CHCH₂ OR, wherein R is alkyl having 1 to 6 carbonsand allyl halides, i.e., CH₂ ═CHCH₂ X, wherein X is chlorine, fluorine,bromine or iodine.

Examples of useful monovinyl monomers include: vinyl esters of aliphaticmonocarboxylic acids, such as, vinyl acetate, vinyl propionate, vinyllaurate, vinyl decanates, vinyl butyrate, vinyl isobutyrate, vinyldimethylpropionate, vinyl ethylbutyrate, vinyl valerate, vinyl caproate,vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinylacetoacetate, vinyl lactate, vinyl β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, and vinylnaphthoate; vinyl ethers, such as, n-butyl vinyl ether, isobutyl vinylether, vinyl propyl ether, vinyl 2-ethylhexyl ether, methyl vinyl ether,butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinylether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethylvinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinylether; vinyl alkoxyalkyl ethers; vinyl haloalkyl ethers; vinyl ketones,such as methyl vinyl ketone, phenyl vinyl ketone and methoxyethyl vinylketone; α-olefins or 1-olefins, such as, ethylene, isobutylene,propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,1-octene, 1-decene, 5-methyl-1-nonene, 5,5-dimethyl-1-octene,4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 5-methyl-1-hexene,4-methyl-1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene,5,6,6-trimethyl-1-heptene, 1-dodecene and 1-octadecene; styrene; styrenederivatives, such as α-propylstyrene, α-ethylstyrene, α-methyl styrene,2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-bromostyrene,3-bromostyrene, 4-bromostyrene, 2-fluorostyrene, 3-fluorostyrene,4-fluorostyrene, 4-nitrostyrene, 2-methoxystyrene, 3-methoxystyrene,4-methoxystyrene, o-methylstyrene (o-vinyl toluene), m-methylstyrene,p-methylstyrene, 2,5-difluorostyrene, 2,5-dichlorostyrene,2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,4,6-trimethylstyrene,4-methoxy-3-methylstyrene, 4-fluoro-3-trifluoromethylstyrene,2-bromo-4-trifluoromethylstyrene, trifluorostyrene, dibromostyrene,iodostyrene, trimethylstyrene, ethylstyrene, diethylstyrene,isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene,decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyreneand ethoxymethylstyrene, allyl monomers, such as, allyl chloride, allylbromide, allyl ethyl ether (CH₂ ═CHCH₂ OC₂ H₅), allyl acrylate, allylcyanide, allyl acetate, allyl benzoate, allyl butyl ether, allyl phenylether, allyl lactate, allyl acetoacetate, allyl stearate, allylpalmitate, and allyl laurate; allylbenzene; and allylbenzenederivatives, such as, 1-allyl-4-bromobenzene, and1-allyl-3,4-dimethyoxybenzene.

Examples of further useful monovinyl monomers include: acrylic acidesters of monohydric alkanols, such as, methyl acrylate, ethyl acrylate,n-butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, n-propylacrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, amylacrylate, hexyl acrylate, octyl acrylate, tert-octyl acrylate,2-phenoxyethyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate,4-chlorobutyl acrylate, cyanoetbyl acrylate, 2-nitroethyl acrylate,benzyl acrylate, methoxybenzyl acrylate, 2-chloro cyclohexyl acrylate,cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate,2-ethoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-butoethylacrylate, 2-(2-methoxyethoxy)ethyl acrylate and 2-(2-butoxyethoxy)ethylacrylate; methylacrylic acid esters of monohydric alkanols, such as,methyl methcarylate, ethyl methacrylate, 2-ethylhexyl methacrylate,cyclohexyl methacrylate, phenyl methacrylate, methyl α-chloroacrylate,n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,isobutyl methacrylate, secbutyl methacrylate, amyl methacrylate, hexylmethacrylate, cyclohexyl methacrylate, benzylmethacrylate, chlorobenzylmethacrylate, octyl methacrylate, N-ethyl-N-phenylaminoethylmethacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, 2-methoxyethylmethacrylate, 3-methoxybutyl methacrylate, 2-propoxyethyl methacrylate,2-ethoxyethyl methacrylate, 2-isopropoxyethyl methacrylate,2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate,2-(2-ethoxyethoxy)ethyl methacrylate and 2-(2-butoxyethoxy)ethylmethacrylate; unsaturated nitriles, such as acrylonitrile (CH₂ ═CHCN),and methacrylonitrile; and heterocyclic vinyl monomers, such as, N-vinylpyrrolidone, N-vinyl carbazole, 2-vinyl-5-ethylpyridine, vinylpyridine(2, 3 or 4), vinylpicoline, N-vinyltriazole,N-vinyl-3,5-dimethylpyrazole, N-vinylcarbazole, vinylthiophene,N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-δ-caprolactam andN-vinyl-2-pyridine.

The compatible divinyl monomers include conjugated dienes andsubstituted divinyl acryl monomers (preferably p-divinyl-benzene) anddiallyl monomers.

Examples of useful divinyl monomers include: o-, m- andp-divinylbenzene; divinyl ether or divinyl oxide [(CH₂ ═CH)₂ O],3,9-divinylspirobi-meta-dioxane, divinyl sulfone (CH₂ ═CHSO₂ CH═CH₂);dienes or conjugated diolefins, such as, propadiene, 1,3-butadiene,1,3-pentadiene (cis and trans), 1,5-hexadiene, 2-methyl-1,3-butadiene(isoprene), and 2,3-methylbutadiene; dicyclopentadiene;2-chloro-1-3-butadiene; and diallyl monomers, such as, diallyl fumarate,diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyldigylcollate, diallyl chlorendate, diallyl adipate and diallyl ether.

Comonomers having three vinyl or allyl reactive moieties, such astriallyl cyanurate, are particularly useful in the crosslinking versionof the invention. Such comonomers can be termed crosslinking boosters,as they speed up the crosslinking and give better results, but as theyare usually expensive, cheaper difunctional comonomers are used as themain crosslinkers.

The vinyl reactive moieties of the end-capped polyarylene polyether andthe vinyl reactive moieties of the comonomers can be substituted, butthe substituents (e.g., Cl) must not be directly on either of the doublebond carbon atoms of the vinyl group (i.e., monovalent unsaturatedorgano group) unless the substituent is alkyl or alkoxy.

Commonly used additives can be used in the homopolymerization andcopolymerization. Wetting and dispersing agents and thickening agents(e.g., carboxymethyl cellulose) can be added. Plasticizers (e.g.,dibutyl phthalate) can also be added. The amounts added will vary uponthe desired results, but preferably each additive is used in the rangeof about 0.1 to 10 percent by weight.

Polymerization (homo- or co-) can be achieved by the use of free radicalinitiators, with or without the aid of heat, or by the use of actinicradiation, such as, ultraviolet radiation. Preferably the free radicalinitiator is a peroxide, and the preferred peroxide is dicumyl peroxide.The polymerization temperature effectively is between 25° (ambienttemperature) and 300° C. and preferably is between 100° and 250° C.

The co- or homopolymerization can be effected using slurry suspension oremulsion type polymerization (with conventional aqueous and non-aqueoussolvents and liquid carriers).

By way of summary, the invention includes oligomers curable by the freeradical mechanism. This is realized by terminating, for example, thepolysulfone chains with reactive unsaturated end-groups. Thepolysulfone-vinyl reactive resins resemble the silane-reactivecounterparts in many physical and mechanical properties, but they donot, however, possess adhesive property. The polysulfone-vinyl reactiveresins are soluble in styrene, and will copolymerize to give a copolymer(usually thermoset) intermediate in Tg. Such polysulfone-vinyl reactiveresin comonomer binder system greatly expands the flexibility in meetingthe cost/performance requirements for different potential end-uses. Thepolysulfone-vinyl reactive resins uses include corrosion-resistancemaxtrix resins or additives, photocurable coatings, powder coatings,magnet wire coatings, polysulfone modifications and fiber reinforcedstructural composites. The data, advantages, methods, etc., concerningthe polysulfone-vinyl reactive resins of the invention set out herein isequally applicable to the generic end-capped polyarylene polyetherresins of the invention.

The following examples are ilustrative of the invention. As used herein,all parts, percentages, ratio and proportions are on a weight basisunless otherwise stated herein or obvious herefrom to one ordinarilyskilled in the art.

Reagents

The following is information on some of the reagents used in thefollowing examples:

    __________________________________________________________________________    Bisphenol A   Union Carbide Corp., bisphenol A,                                             99.71 percent purity. Used without                                            further purification.                                           Sulfone Monomer                                                                             ICI sulfone monomer, 100 percent                                              purity assumed.                                                 Vinyl benzyl chloride                                                                       Dow NC-1915, 98 plus percent purity,                                          40 percent para-/60 percent meta-                                             isomer ratio.                                                   2-chloroethyl acrylate                                                                      Haven Chemical, 95 plus percent                                               purity, inhibited with 0.5 percent                                            of hydroquinone.                                                2-chloroethyl same as immediately above.                                      methacrylate                                                                  2-chloroethyl vinyl                                                                         Polysciences, P. p. 109° -110° C.                 ether                                                                         Allyl Chloride                                                                              Matheson Coleman and Bell B.p. 45° -46° C.        Methacryloyl Chloride                                                                       Polysciences, B.p. 95° -96° C.                    Dimethyl Sulfoxide                                                                          Matheson Coleman and Bell.                                      (DMSO)                                                                        Monochlorobenzene (MCB)                                                                     Matheson Coleman and Bell.                                      Sodium Hydroxide                                                                            Mallinckrokt Chemical Works,                                                  98.5 percent purity.                                            Lupersol-130  2,5-dimethyl-2,5-di(t-butyl peroxy)                                           hexyne-3.                                                       Atlac 382-05A Commercial chemical-resistant                                                 corrosion-resistant grade of polyester                                        (thermosetting), ICI, Wilmington, Del.                          Stypol-2995   Commercial polyester resin, Freeman                                           Chemical Corp., Port Washington, Wisc.                          UDEL ® Polysulfone                                                                      Commercial tough, rigid, high-strength,                                       thermoplastic polysulfone end-terminated                                      with methoxy moieties, Union Carbide,                                         New York, New York. Polysulfone P-1700                                        is one of a line of UDEL ® polysulfones                                   commercially available from Union Carbide.                                    Polysulfone P-1700 is composed of the                                         recurring units of formula I above                                            (see page 5) with methoxy end-capping                                         moieties.                                                       __________________________________________________________________________

Analytical Methods Determination of Amount of End-Capping Agent Needed

The amount of end-capping reagent needed, on a 20 percent excess basis,can be calculated from the following equation: ##EQU1## whereinM=molecular weight of end-capping reagent,

N_(HCl) =normality of HCl/DMSO solution,

V_(HCl) =volume of HCl/DMSO used in ml,

W_(t) =total weight of reaction mixture in gm,

W_(s) =sample weight in gm, and

P_(s) =purity of end-capping reagent.

DMSO is dimethyl sulfoxide.

This information is needed for determining the amount of reagentrequired for the end-capping reaction. A titration method is used forthis purpose.

Upon completion of the polymerization step, a small sample (about 2 to 3gm) of the reaction mixture is quickly taken from the vessel and placedin a 250 ml Erlenmeyer flask. The sample is weighed and a 50 ml solutionof DMSO/MCB (1/1) is introduced (MCB is monochlorobenzene). The samplesolution is heated gently on a hot plate until dissolution is complete.A drop of bromocresol purple indicator (0.5 percent in methanol) isadded and the sample is titrated with a 0.1N HCL solution (in DMSO) to ayellow end point (pH 5.2 to 6.8). Duplicate tests should be made.

Test For Completion Of The End-Capping Reaction

A 1 to 2 gm sample of the reaction mixture is introduced into a 250 mlErlenmeyer flask containing a 50 ml solution of DMSO/MCB (1/1). Thesample solution is heated on a hot plate until dissolution is complete.Two drops of the bromocresol purple solution are added. The reaction iscomplete if the indicator turns greenish yellow or yellow. Otherwise,the color will be blue indicating the presence of unreacted phenolateend groups.

Glass Transition Temperature Determination

The glass transition temperature (T_(g)) was measured with a DuPont 990instrument fitted with pressure DSC cell at a heating rate of 10° C. perminute under a nitrogen pressure of 600 psig. (DCS is DifferentialScanning Calorimeter; the procedure for using it is described in A.Duswalt, "Industrial Research," July 1975, pp. 42-45.) Comparable valuescan also be obtained from the temperature-modulus data measured with anInstron machine at a heating rate of 1.5° C. per minute.

Melting Point Determination

When heated in a capillary melting point apparatus (e.g., aThomas-Hoover capillary apparatus), phase transition of apolysulfone-vinyl reactive resin can be visually observed. This test isuseful for a rapid but rough identification of a polysulfone-vinylreactive resin.

Mn Determination

The number average molecular weight (Mn) of the polysulfone-vinylreactive resins is determined by NMR technique using a Varian 100 MHZNMR Instrument. Assuming the polysulfone-vinyl reactive resins arecompletely endcapped, i.e., each molecule is terminated with twounsaturated organo end groups, and there is no hydrolysis of the endgroups, they are represented by the following general formula: ##STR22##wherein n is the number average degree of polymerization.

PSF-VR/Comonomer Binder System--Peroxide Curing

Compounding--The peroxide, usually DiCup, was dissolved in the liquidcomonomer, and was subsequently mixed with the polysulfone-vinylreactive resin fluff. When the two components were immiscible, a commonsolvent of low boiling point, such as acetone, was used to give ahomogeneous solution before blending with the resin fluff. The solventwas removed by air drying. The latter method usually provides a moreuniform mixture, but some comonomer may be lost due to evaporation.

Curing--Unless otherwise specified, all test specimens were cured bycompression molding at 160° C. for a ten-minute cycle. These conditionswere chosen arbitrarily and may not be optimum for all the bindersystems studied.

PSF-VR/Comonomer Binder System--Electron Beam Curing

Sample Preparation--A 4"×4"30 mil plaque was employed for theelectron-beam curing. The plaque was prepared by compression molding ofa thoroughly blended mixture of the polysulfone-vinyl reactive resin andcomonomer. A mild molding temperature, usually around 160° C., was usedto prevent premature gellation of the formulation.

Irradiation--A two-million volt van de Graaf electron accelerator wasused as the source of electron beam radiation. Different irradiationdoses were achieved by varying the exposure time.

PSF-VR/Comonomer Binder System--- Photocuring

Sample Preparation--A formulation, usually containing apolysulfone-vinyl reactive (PSF-VR) resin, a comonomer and aphoto-initiator, was thoroughly mixed and was compression-molded to a 10mil thick film. By using a molding temperature at or below 160° C., theresulting film remained thermoplastic. The film was mounted on an8"×8"×5 mil aluminum foil to facilitate handling.

U.V. Irradiation--Linde photocuring equipment, having a flux density of160 watts/ft², was used as the U.V. source. Different irradiation doseswere accomplished by varying the conveyor speed and the number of passesthrough the irradiation zones.

Gel Content (Or Percent Extractables)

The gel contents of the cured polysulfone-vinyl reactive resin sampleswere measured by solvent extraction in boiling chloroform. The data ofpercent extractables shown in Tables XVI and XVIII were determined inmethylene chloride. The higher the cross-linking is,the greater the gelcontent and the lower the percent extractables.

Swelling Index

Swelling index may be related quantitatively to the cross-linkingdensity of a given network structure. The data shown in Table XVII andXVIII were values measured in methylene chloride and calculatedaccording to the following equation: ##EQU2##

Environmental Stress-Crack Resistance

Environmental stress-crack resistance data were measured at constantstress levels using an environment of solvent-saturated cotton swabattached to the specimen. Performance was rated on the basis of timeelapsed before rupture at a given stress level.

Solution Polymerization

The desired amounts of polysulfone-vinyl reactive resin and freshlydistilled styrene monomer were placed into a pyrex glass ampoule. Asolution made of freshly distilled monochlorobenzene and benzoylperoxide (1.67 mg. benzoyl peroxide/1 ml monochlorobenzene)was added sothat the final solution contained 20 percent of reactants and 0.1percent of benzoyl peroxide. The ampoule was degassed at liquid nitrogentemperature and was sealed under a nitrogen atmosphere. Polymerizationwas carried out at 80° C. for a period of 19 hrs. At the end ofpolymerization, the ampoule was opened and the polymer recovered bycoagulation in isopropanol.

Reduced Viscosity Determination

The reduced viscosity (R.V.) is determined by the procedure ofASTM-D-2857 at a concentration of 0.2 grams of the resin in 100milliliters of solution.

The above information often uses the term polysulfone-vinyl reactiveresins but is equally applicable to or encompasses the broader termmonovalent, unsaturated organo end-capped polyarylene polyether resins.

EXAMPLE 1 Allyl Terminated Polysulfone Oligomer

To a five-liter four-neck flask was charged 456.56 grams (2.0 mole) ofbisphenol A, 1 liter of dimethyl sulfoxide (DMSO), 2 liters ofchlorobenzene and 320.0 g (4.0 mole) of 50 percent sodium hydroxidesolution. The resulting mixture was heated to reflux and the waterdehydrated using the chlorobenzene/water azeotrope with recycle of thechlorobenzene. After complete dehydration, the chlorobenzene was removeduntil the pot temperature reached 149° C. At this point, 553.5 g (1.93mole) of 4,4'-dichlorodiphenyl sulfone dissolved in 560 grams ofchlorobenzene was added and the reaction allowed to proceed at 137° to160° C. with removal of the chlorobenzene. Two hours past the additionof the sulfone monomer (the hydroxy terminated polysulfone having beenformed), the reaction was cooled to 60 and 40 grams of allyl chlorideadded. In 5 minutes, an additional 10.0 grams of 50 percent sodiumhydroxide solution was charged and then heated to 110° C. for 1 hour.Oxalic acid (10 g) was added to acidify the reaction, 2 liters ofchlorobenzene was added to cut the viscosity and the solution wasfiltered to remove sodium chloride. The filtrate containing the productwas washed seven times with 1.4 liters of water to remove the DMSO andthe product was then recovered by processing through a vented extruderat 300° C. to afford 620 grams of pelletized, allyl-terminatedpolysulfone oligomer.

EXAMPLE 2 Thermosetting 5,000 Molecular Weight Vinyl End-CappedPolysulfone

To a 3-liter round bottom flask was added 300 9grams of the hydroxyterminated polysulfone (Mn=5,000), 500 ml of chlorobenzene and 1000 mlof DMSO. The hydroxy terminated polysulfone was prepared from bisphenolA and 4,4'-dichlorodiphenyl sulfone as described in Example 1. To thissolution at room temperature was added dropwise 9.7 gms of 49.6 percentsodium hydroxide (0.12 moles). The reaction mixture darkenedsignificantly on addition of caustic. Then 18.96 g (20 percent excess)of vinyl benzyl chloride (commercially available from Dow Chemical) wasadded dropwise. The solution was stirred at 3 for 3 hours and at 70° C.for 2 hours. The contents were still basic (pH≃8) after settingovernight at room temperature. Oxalic acid was added until a pH of 3 wasobtained. Coagulation of 200 ml of the solution in 1500 ml of methanol,and drying overnight in a vacuum oven (60 mm) at 120° C. yielded a vinylbenzyl end-capped polysulfone (5,000 molecular weight). The sample wascompression molded at 250° C./10 minutes. The resulting 25 mil plaquehad a tensile modulus of 248,000 psi, tensile strength of 3,040 psi,elongation to break is 1.2 percent, and pendulum impact of 2.4 ft.lb./in.³. Environmental stress aging tests at 200 psi indicated that thesample was intact in acetone, toluene and trichloroethylene for over 25minutes. The material, however, swelled in trichloroethylene.

EXAMPLE 3 Thermosetting 10,000 Molecular Weight Vinyl Benzyl End-CapedPolysulfone

A vinyl benzyl end-capped polysulfone (10,000 molecular weight) wasprepared as in Example 2 above, except that in this preparation ahydroxy terminated polysulfone oligomer (10,000 molecular weight) wasemployed. The hydroxy terminated polysulfone oligomer was prepared frombisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example 1.The vinyl end-capped polymer was compression molded at 250° C. for 10minutes. A 15 mil plaque exhibited a tensile modulus of 320,000 psi, atensile strength of 11,000 psi, an elongation to break of 6 percent anda pendulum impact of 27 ft. lb./in.³. At 200 psi, it took 480 sec. forfailure of the sample in trichloroethylene. In acetone and toluene, thefailure was instantaneous. A significant resistance to trichloroethyleneis useful in some electrical applications.

EXAMPLE 4 Coating Systems Based on Allyl Terminated Polysulfone

Allylic terminated polysulfone prepared as in Example 1 above wasdissolved in methylene chloride solvent to provide a 10 percentsolids-containing solution. Several steel "D" plates, 10 mils thick,were dip coated in this solution and dried at room temperature for 10minutes which was followed first by, oven drying at 125° C. for 45minutes and then by various high temperature oven time bake exposures at315° to 320° C.

Upon weighing the residual coating baked onto the steel, the coatingswere subjected to CH₂ Cl₂ extraction by immersion in the stirred solventbath. The appropriate graph in FIG. 1 illustrates that the degree ofsolubility to methylene chloride is an inverse function of bake timeexposure in an oven at 315° to 320° C. Similar extraction data followingthe identical procedure outlined above was obtained for glass and chromesubstrates coated allylic terminated polysulfone (prepared as in Example1 above) and for controls which had P-1700 polysulfone coatings. Theappropriate graph in FIG. 1 illustrates the methylene chloridesolubility curve for the glass-plated substrates; and the graph in FIG.2 illustrates the methylene chloride solubility curve for thechrome-plated substrates. Steel "D" plates coated with either P-1700polysulfone coatings or the allyl-terminated polysulfone (prepared as inExample 1) were subjected to acetone and methylene chloride extractionby immersion. The data and results are set out below in Table II:

                  TABLE II                                                        ______________________________________                                                  POLY-     SOLVENT                                                             SULFONE   AND                                                       SUBSTRATE TYPE      TREATMENT   RESULTS                                       ______________________________________                                        Steel "D" P-1700    Acetone,    Stress cracked                                Plate               1 minute    coating.                                                          immersion.                                                          Allyl     Acetone,    No effect.                                              Terminated                                                                              1 minute                                                                      immersion.                                                          P-1700    Methylene   Coating dissolved.                                                Chloride,                                                                     10 minute                                                                     immersion.                                                          Allyl     Methylene   No effect.                                              Terminated                                                                              Chloride,                                                                     10 minute                                                                     immersion.                                                          P-1700    Acetone,    Coating dissolved.                                                10 minute                                                                     immersion.                                                          Allyl     Acetone,    No effect.                                              Terminated                                                                              10 minute                                                                     immersion.                                                ______________________________________                                    

The data of Table II shows that acetone and methylene chloride immersioncaused stress cracking or dissolution of the P-1700 polysulfonecoatings, but did not have any effect on the allylterminated polysulfonecoatings of this invention. Several samples of aluminum sheet (7.5 milsthick, type 3003 H 14) were also coated as described in the procedureabove and baked. The coated aluminum plates were subjected to acetoneand methylene chloride extraction by immersion, in some cases followedby dipping in hot sodium hydroxide solution. A comparison of the solventresistance (data and results) of allyl terminated polysulfone andconventional P-1700 polysulfone is set out below in Table III:

                  TABLE III                                                       ______________________________________                                                POLY-     SOLVENT                                                     SUB-    SULFONE   AND                                                         STRATE.sup.1                                                                          TYPE      TREATMENT   RESULTS                                         ______________________________________                                        Aluminum                                                                              P-1700    1 minute in Aluminum attacked.                                                Acetone                                                                       followed by                                                                   15 sec. dip                                                                   in 20% NaOH                                                                   solution.                                                           Allyl     1 minute in No effect.                                              Terminated                                                                              Acetone                                                                       followed by                                                                   15 sec. dip                                                                   in 20% NaOH                                                                   solution.                                                           P-1700    10 minutes in                                                                             Coating removed;                                                  CH.sub.2 Cl.sub.2                                                                         all metal attacked.                                               followed by                                                                   hot NaOH                                                                      solution.                                                           Allyl     10 minutes in                                                                             No effect.                                              Terminated                                                                              CH.sub.2 Cl.sub.2                                                             followed by                                                                   hot NaOH                                                                      solution.                                                           P-1700    10 minute   Stress cracked                                                    immersion   coating.                                                          in                                                                            Acetone.                                                            Allyl     10 minute   No effect.                                              Terminated                                                                              immersion                                                                     in                                                                            Acetone.                                                    ______________________________________                                         Note:                                                                         .sup.1 All substrates were given at least one 90° bend in the test     coupon prior to solvent resistance testing.                              

The data of Table III shows that acetone and methylene chlorideimmersion caused stress cracking or coating removal of the P-1700polysulfone coatings, but did not have any effect on theallyl-terminated polysulfone coatings of this invention. Dipping in hotsodium hydroxide solution, after the solvent immersion step, had noeffect with the allyl-terminated polysulfone coatings but did attach thealuminum substrates associated with the P-1700 polysulfone coatings.

Both the allylic-terminated polysulfone and P-1700 polysulfone coatingsreleased from glass substrates after baking when exposed to hotdetergent solutions (80° C.--14 minutes). On one case, the contol P-1700did not show chlorinated solvent resistance whereas the allyl terminatedand baked coating provides solvent resistance (chlorinated and acetone)yet may be readily removed with hot detergent solutions.

EXAMPLE 5

Into a four-necked, two-liter Morton Flask, equipped with a mechanicalstirrer, water trap, condenser, thermometer, addition funnel, and argoninlet, there was placed 183.16 gm of bisphenol A (0.8 mole), 550 ml ofDMSO and 700 ml of monochlorobenzene (MCB). The slurry was heated toabout 80° C. to give a clear solution. An aqueous solution of 64.96 gmof sodium hydroxide (98.5 percent purity, 1.6 mole) in 75 ml ofdistilled water was introduced. Azeotropic distillation began at 119° C.and was continued until the temperature reached 155° C. in 4 hrs. Duringthis period a total of 792.2 gm of distillate was collected, whichcontained 135 ml of aqueous layer. The reaction vessel was cooled to140° C. and a hot solution of 208.86 gm (0.728 mole) of4,4'-dichlorodiphenylsulfone (sulfone monomer) in 250 ml ofmonochlorobenzene was introduced rapidly into the reaction vessel.Distillation of monochlorobenzene resumed until the reaction temperatureattained 165 ° C. when in additional 319 gm of monochlorobenzene wasdistilled off. The polymerization was maintained at this temperature foran additional 90 minutes. Material balance

    ______________________________________                                                    Reactor Charge                                                                            Water-trap                                            Material    gm          Discharge, gm                                         ______________________________________                                        Bisphenol A 183.16                                                            Sulfone monomer                                                                           208.86                                                            NaOH solution                                                                             139.96      (mainly MCB + water)                                  DMSO        589.60                                                            MCB         1,050.70                                                          Total       2,172.28    1,111.20                                              ______________________________________                                    

There was 1,061.08 gm of reaction mixture remaining in the vessel andthe polysulfone oligomer concentration was about 38 percent.

Samples were drawn from the reaction vessel for sodium phenolateend-group analysis. The amount of vinyl benzyl chloride required on a 22percent excess basis was found to be 30.8 gm (0.198 mole).

The reaction mixture was brought to a temperature of 115° C., and asolution of vinyl benzyl chloride (the end-capping reagent) in 30 ml drymonochlorobenzene was introduced. The reaction was kept at thistemperature for 90 min. until the bromocresol purple test becameyellowish in color. Thereafter, the reaction was stopped, and thereaction mixture was cooled down to room temperature. The hazy, viscoussolution was diluted with 600 ml of monochlorobenzene and was filteredto remove the salt. The clear, amber-colored filtrate was poured into aWaring blender containing a large excess amount of isopropanol (ormethanol) to coagulate the polysulfone-vinyl reactive PSF-VR resin whichwas washed twice more with isopropanol, filtered and was dried undervacuum at 75° C. to yield a white, powdery solid.

    ______________________________________                                        Product recovered  311 gm (91 percent of                                                         theoretical)                                               Reduced viscosity, R.V.                                                                          0.17                                                       (chloroform, 25° C.)                                                   Melting point      160° C.                                             ______________________________________                                    

EXAMPLE 6

Using the procedures described in Example 5 but with the followingstarting materials,

    ______________________________________                                        Bisphenol A        183.16 gm (0.8 mole)                                       Sulfone monomer (4,4'-di-                                                                        220.34 gm (0.768 mole)                                     chlorodiphenyl sulfone)                                                       Sodium hydroxide    64.96 gm (1.6 mole)                                       2-chloroethyl methacrylate                                                                        11 gm (0.0703 mole, 25                                                        percent excess)                                           ______________________________________                                    

a white powdery polysulfone-vinyl reactive resin having methacryloxyethoxy end-groups was prepared.

    ______________________________________                                        Product recovered   313 gm (90 percent of                                                         theoretical)                                              R.V. (chloroform, 25° C.)                                                                  0.25                                                      Melting point       180° -183° C.                               ______________________________________                                    

EXAMPLE 7

Using the procedures described in Example 5 but with the followingstarting materials,

    ______________________________________                                        Bisphenol A        183.16 gm (0.8 mole)                                       Sulfone monomer (4,4'-di-                                                                        208.86 gm (0.728 mole)                                     chlorodiphenyl sulfone)                                                       Sodium hydroxide    64.96 gm (1.6 mole)                                       Allyl chloride      21.37 gm (0.279 mole,                                                         100 percent excess)                                       ______________________________________                                    

a white, powdery polysulfone-vinyl reactive resin having alloxyend-groups was obtained.

    ______________________________________                                        Product recovered   306 gm (90 percent of                                                         theoretical)                                              R.V. (chloroform, 25° C.)                                                                  0.20                                                      Number average molecular                                                                          6,540                                                     weight (--M.sub.n )                                                           Melting point       163-165° C.                                        ______________________________________                                    

EXAMPLE 8

Using the procedures described in Example 5 but with the foIlowingstarting materials,

    ______________________________________                                        Bisphenol A        183.16 gm (0.8 mole)                                       Sulfone monomer (4,4-'di-                                                                        220.33 gm (0.768 mole)                                     chlorodiphenyl sulfone)                                                       Sodium hydroxide    64.96 gm (1.6 mole)                                       2-chloroethyl acrylate                                                                            8.6 gm (0.0607 mole,                                                          10 percent excess)                                        ______________________________________                                    

a white, fluffy polysulfone-vinyl reactive resin having acryloxy ethoxyend-groups was prepared.

    ______________________________________                                        Product recovery    306 gm (88 percent of                                                         theoretical)                                              R.V. (chloroform, 25° C.)                                                                  0.30                                                      Melting point       170° -190° C.                               ______________________________________                                    

EXAMPLE 9

Table IV below sets out several representative polysulfone-vinylreactive resins of the invention, plus certain information concerningtheir preparation and some of their properties:

                                      TABLE IV                                    __________________________________________________________________________    PREPARATION AND CHARACTERIZATION OF                                           REPRESENTING LABORATORY-PREPARED PSF-VR.sup.(a) RESINS                                     Sulfone/Bis A R.V.                                               End-Capping  Charge Ratio.sup.(d)                                                                  Recovery                                                                            Chloroform                                                                          T.sub.m.sup.(b)                              Reagent      Mole/Mole                                                                             %     25° C.                                                                       °C.                                                                         --M.sub.n                               __________________________________________________________________________    2-chloroethylmethacrylate                                                                  0.93    88    0.22  165°-175°                                                              11,560.sup.(c)                                     0.93    92    0.21  163°-177°                                    0.944  96    0.21  180°-185°                                    0.944  92    0.21  180°-190°                                   0.96    89    0.25  177°-196°                                   0.96    92    0.25  180°-183°                                   0.98    93    0.35  210°-212°                      2-chloroethylacrylate                                                                      0.93    89    0.23  160°-173°                                   0.96    88    0.30  170°-190°                      methacryloyl chloride                                                                      0.93    90    0.25  175°-190°                                                            10,600                                  vinyl benzyl chloride                                                                      0.91    97    0.16  159°-160°                                   0.91    93    0.17  158°-162°                                   0.93    94    0.19  172°-174°                                   0.96    91    0.25  178°-182°                      vinyl benzyl chloride                                                                      0.96    92    0.25  191°-195°                                   0.98    88    0.37  206°-210°                                   0.98    91    0.35  198°-200°                      allyl chloride                                                                             0.91    90    0.20  163°-165°                                                             6,540                                  2-chloroethyl vinylether                                                                   0.91    88    0.20  170°-173°                      __________________________________________________________________________     Notes:                                                                        .sup.(a) Polysulfonevinyl reactive.                                           .sup.(b) Polymer softens and melts gradually within the temperature range     .sup.(c) Abnormally high value due to incomplete endcapping.                  .sup.(d) The hydroxy terminated polysulfones which were vinyl endcapped       were prepared from bisphenol A and 4,4dichlorodiphenyl sulfone as             described in Example 1.                                                  

The 0.22 RV, 2-chloroethyl methacrylate end-capped polysulfone-vinylreactive resin shown in Table IV is an example of low end-cappingefficiency. Its deficiency is reflected by the higher than expectednumber average molecular weight (M_(n)) value calculated on theassumption of 100 percent end-capping efficiency. Such a resin maycontain up to 30 percent of non-curable fraction as evidenced by solventextraction test. When the above mentioned precautions are observedduring the preparation, however, this difficulty may be largelyalleviated.

It has been found that, analogously to the behavior ofpolysulfone-silane reactive resins, glass transition temperature (Tg) ofa polysulfone-vinyl reactive resin increases with increasing molecularweight and, eventually, approaches that of the standard polysulfone.FIG. 4 shows the above relationship for a series of vinyl benzyloxyend-capped polysulfone-vinyl reactive resins. (The hydroxy terminatedpolysulfones which were vinyl end-capped were prepared from bisphenol Aand 4,4'-dichlorodiphenyl sulfone as described in Example 1.) The hollowcircles indicate the Tg values of the virgin samples. In each instancethe virgin sample was heated to a temperature of 217° C., cooled, andthen measured again to study the effect of thermal history. The secondreading was often found to be several degrees higher, which is a sign ofresin advancement. Above the Tg, there is a rubbery polymer; below theTg, there is a glassy polymer.

EXAMPLE 10

Polysulfone-vinyl reactive resins containing (a) vinyl ether ethoxyend-groups, (b) methacryloxy ethoxy end-groups and (c) vinyl benzyloxyend-groups were subjected to thermal abuse at several temperatures. (Thehydroxy terminated polysulfones which were vinyl end-capped wereprepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as describedin Example 1.) Table V below illustrates the differences in reactivitiesof such resins.

                  TABLE V                                                         ______________________________________                                        EFFECT OF END-GROUP TYPE ON THE REACTIVITY                                    OF POLYSULFONE-VINYL REACTIVE                                                                       R.V..sup.(a) After 10 min.                                            Initial Heating at (% Gel).sup.(b)                              Type of End-Group                                                                           R.V.    160° C.                                                                          200° C.                                                                      220° C.                          ______________________________________                                        Vinyl Ether Ethoxy                                                                          0.17    0.173     0.176 0.174                                   Methacryloxy Ethoxy                                                                         0.193   0.197     0.206 0.207                                   Vinyl Benzyloxy                                                                             0.172   (5.1)     (55.1)                                                                              (76.2)                                  ______________________________________                                         Notes:                                                                        .sup.(a) Measured in chloroform at 25° C.                              .sup.(b) Gel content determined by extraction test with boiling               chloroform.                                                              

EXAMPLE 11

Several typical polysulfone-vinyl reactive resin/comonomer systems wereprepared using heat-peroxide curing. (The hydroxy terminatedpolysulfones which were vinyl end-capped were prepared from bisphenol Aand 4,4'-dichlorodiphenyl sulfone as described in Example 1.) Theformulations and curing conditions used in this work for thepolysulfone-vinyl reactive comonomer binder systems, as well as theappearance of the system and the stress-crack resistance of the systemto acetone, are shown in Table VI below.

                                      TABLE VI                                    __________________________________________________________________________    PEROXIDE (HEAT) CURING OF PSF-VR.sup. (a) /COMONOMER BINDER SYSTEMS                         Methacryloxy                                                                         Methacryloxy                                                                          Methacryloxy                                                                         Vinyl  Vinyl Vinyl  Acryloxy              PSF-VR.sup. (a), End-Gp. Type                                                               Ethoxy Ethoxy  Ethoxy Benzyloxy                                                                            Benzyloxy                                                                           Benzyloxy                                                                            Ethoxy                __________________________________________________________________________    R. V. dl/g    0.35   0.25    0.25   0.25   0.25  0.25   0.23                  Comonomer (% By wt)                                                                         Styrene                                                                              Styrene Styrene                                                                              Styrene                                                                              Styrene                                                                             Diacetone                                                                            Styrene (17)                        (17)   (17)    (39)   (17)   (17)  Acryla-                                                                       mide (20)                    Curing Conditions                                                                           160° C.                                                                       160° C.                                                                        160° C.                                                                       160° C.                                                                       160° C.                                                                      210° C.                                                                       160° C.                      15 min.                                                                              25 min. 25 min.                                                                              25 min.                                                                              15 min.                                                                             10 min.                                                                              30 min.                             Dicup.sup.(b)                                                                        Dicup   Dicup  Dicup  Dicup Lupersol                                                                             t-Butyl                             1.7%   1.7%    1.7%   1.7%   1.7%  130, 1%                                                                              perbenzoate           Gel Content, %                                                                              73     96      89     95     91    98     75                    Appearance    clear, clear,  clear  clear, clear,                                                                              yellowish,                                                                           clear                               transparent,                                                                         transparent,                                                                          transparent,                                                                         transparent                                                                          transparent                                                                         fairly transparent,                        and tough                                                                            and tough                                                                             somewhat                                                                             and tough                                                                            and tough                                                                           transparent                                                                          tough                                              brittle             fairly tough                 Stress-crack  good   good    fair-good                                                                            good   good  good   good                  Resistance to                                                                 Acetone                                                                       __________________________________________________________________________     Notes:                                                                        .sup.(a) Polysulfonevinyl reactive                                            .sup.(b) Dicumyl peroxide                                                

EXAMPLE 12

Some of the thermal and mechanical properties of a representative numberof polysulfone-vinyl reactive/comonomer binder systems are set out inTable VII below. (The hydroxy terminated polysulfones which were vinylend-capped were prepared from bisphenol A and 4,4'-dichlorodiphenylsulfone as described in Example 1.) All of the copolymer samples, unlessotherwise specified, were prepared from a mixture containing 17.4percent by weight of comonomer and 80.9 percent of polysulfone-vinylreactive resin. Curing was effected by compression molding at 160° C. inthe presence of dicumyl peroxide (1.7 percent).

                                      TABLE VII                                   __________________________________________________________________________    THERMAL AND MECHANICAL PROPERTIES OF                                          REPRESENTING PSF-VR.sup.(a) /COMONOMER BINDER SYSTEMS.sup.(b)                 __________________________________________________________________________    (c)                                                                                              a-Methyl                                                                            Methyl        Ethyl Hydroxypropyl                    Comonomer Type                                                                             Styrene                                                                             Styrene                                                                             Methacrylate                                                                         Acrylonitrile                                                                        Fumarate                                                                            Methacrylate                     __________________________________________________________________________    PSF-VR.sup.(a), End-Gp. Type                                                               Vinyl Vinyl Vinyl  Vinyl  Vinyl Vinyl                                         benzyloxy                                                                           benzyloxy                                                                           benzyloxy                                                                            benzyloxy                                                                            benzyloxy                                                                           benzyloxy                        R.V. dl/gm   0.17  0.17  0.17   0.17   0.16  0.16                             Color        colorless                                                                           colorless                                                                           colorless                                                                            yellow colorless                                                                           colorless                        Clarity.sup.(d)                                                                            transparent                                                                         transparent                                                                         transparent                                                                          transparent                                                                          transparent                                                                         transparent                      Tg °C.                                                                              140°                                                                         150°                                                                         160°                                                                          155°                                                                          105°                                                                         130°                      Modulus at 250° C., psi                                                             310   360   310    730    105   400                              Tensile Strength, psi                                                                      10,400                                                                              9,180 11,000 11,000 4,000 5,000                            Tensile Mod- 2.99  3.29  3.25   3.14   3.23  3.00                             ulus, psi × 10.sup.-6                                                   Elongation at break, %                                                                     8     4     5.5    6      1.5   2.2                              Pendulum Impact, ft-lb/in.sup.3                                                            34    34    35     25     12    16                               __________________________________________________________________________                 2-chloroethyl     2-Ethylhexyl                                   Comonomer Type                                                                             Methacrylate                                                                         Diacetone Acrylamide                                                                     Acrylate                                                                             Ethyl Acrylate                                                                        Vinyl Acetate                   __________________________________________________________________________    PSF-VR.sup.(a), End-Gp. Type                                                               Vinyl benzyloxy                                                                      Vinyl benzyloxy                                                                          Vinyl benzyloxy                                                                      Vinyl benzyloxy                                                                       Vinyl benzyloxy                 R.V. dl/gm   0.16   0.25       0.16   0.16    0.16                            Color               yellow     colorless                                                                            colorless                                                                             colorless                       Clarity.sup.(d)     transparent                                                                              transparent                                                                          transparent                                                                           transparent                     Tg °C.                                                                              120°                                                                          155°                                                                              120°                                                                          130°                                                                           150°                     Modulus at 250° C., psi                                                             1,000  150        300    400     570                             Tensile Strength, psi                                                                      5,640  9,950      10,300 9,000   9,620                           Tensile Mod- 3.13   2.60       3.26   2.78    3.06                            ulus, psi × 10.sup.-6                                                   Elongation at break, %                                                                     2.2    8          5.5    6       5                               Pendulum Impact, ft-lb/in.sup.3                                                            7      15         11     30      9                               __________________________________________________________________________     Notes:                                                                        .sup.(a) Polysulfonevinyl reactive                                            .sup.(b) All specimens cured by compression molding at 160° C.         .sup.(c) Each formulation contained 17.4 percent of comonomer.                .sup.(d) The degree of transparency may vary considerably.               

EXAMPLE 13

Some of the thermal and mechanical properties of more polysulfone-vinylreactive resin/comonomer compositions, but with comonomers containingmultiple unsaturation, are set out in Table VIII below. (The hydroxyterminated polysulfones which were vinyl end-capped were prepared frombisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example1.) These comonomers, in theory, should result in network structures ofmuch higher crosslinking densities. Even though the polysulfone-vinylreactive resin exhibited only limited solubility at room temperature inmany of the comonomers studied, in most instances the molded plaquepossessed a good clarity and a single glass transition temperaturecharacteristic of a copolymer.

Because of questionable compositional uniformity achieved in thepreparation of these blends, the true loading of a comonomer in a testspecimen may vary significantly from the value indicated. This isthought to be reflected by some erratic glass transitional temperaturevalues. Roughly speaking, however, the glass transitional temperature ofthe cured compositions varied according to those of homopolymers derivedfrom the corresponding comonomers as well as the comonomer loadings.

Because of their thermoset nature, the cured resins exhibited a markedlyimproved environmental stress-crack resistance and a better dimensionalstability at elevated temperatures than those of the thermoplasticpolysulfone.

                                      TABLE VIII                                  __________________________________________________________________________    THERMAL AND MECHANICAL PROPERTIES OF                                          REPRESENTATIVE PSF-VR.sup.(a) /MULTI-FUNCTIONAL                               CO-MONOMER BINDER SYSTEMS.sup.(b) (c)                                                                                     Trimethylol-                                                                         Styrene/                                                                            Styrene/                                            Diallyl                                                                             Ethylene                                                                             propane                                                                              Divinyl                                                                             Polymeric                         Divinyl  Divinyl  Isophtha-                                                                           Dimethacry-                                                                          Trimethacry-                                                                         Benzene                                                                             Booster.sup.(f)      Co-Monomer Type.sup.(d)                                                                    Benzene (17.4).sup.(e)                                                                 Benzene (17.4)                                                                         late (17.4)                                                                         late (17.4)                                                                          late (17.4)                                                                          (18.5/15.4)                                                                         (14.4/13.4)          __________________________________________________________________________    PSF-VR.sup.(a), End-Group                                                                  Vinyl    Vinyl    Vinyl Vinyl  Vinyl  Vinyl Vinyl                Type         benzyloxy                                                                              benzyloxy                                                                              benzyloxy                                                                           benzyloxy                                                                            benzyloxy                                                                            benzyloxy                                                                           benzyloxy            R.V. dl/gm   0.17     0.17     0.17  0.16   0.16   0.17  0.17                 Color        colorless                                                                              colorless                                                                              colorless                                                                           colorless                                                                            colorless                                                                            colorless                                                                           colorless            Clarity.sup.(g)                                                                            transparent                                                                            transparent                                                                            transparent                                                                         transparent                                                                          transparent                                                                          transparent                                                                         transparent          Tg °C.                                                                              170°                                                                            165°                                                                            115°                                                                         148°                                                                          160°                                                                          155°                                                                         165°          Modulus at 250° C.                                                                  800      450      400   1,050  310    1,230 380                  Tensile Strength, psi                                                                      11,300   4,690    11,400                                                                              5,530  4,560  12,100                                                                              8,120                Tensile Modulus,                                                                           3.15     3.25     3.55  3.10   3.13   3.42  3.15                 psi × 10.sup.-6                                                         Yield Elongation, %                                                                        --       --       5.5   --     --     --    --                   Elongation at break, %                                                                     6.0      2.5      5.8   1.9    1.7    6.5   3.5                  Pendulum Impact ft-lb/in.sup.3                                                             44       5        14    20     6      24    28                   __________________________________________________________________________     Notes:                                                                        .sup.(a) Polysulfonevinyl reactive.                                           .sup.(b) Peroxide cured.                                                      .sup.(c) All specimens cured by compression molding at 160° C.         unless otherwise specified.                                                   .sup.(d) Percent by weight of comonomer added.                                .sup.(e) Post cured at 200° C. for 10 min.                             .sup.(f) A polymeric booster containing both pendant and terminal vinyl       groups.                                                                       .sup.(g) The degree of transparency may very considerably.               

EXAMPLE 14

By employing polysulfone-vinyl reactive resins of various initialmolecular weights, polysulfone-vinyl reactive comononer binder systemshaving different cross-linking densities as well as polysulfone blocklengths can be prepared. The effect on the properties three compositionswhich are otherwise identical except for the above-mentioned aspects,are set out in Table IX below. (The hydroxy terminated polysulfoneswhich were vinyl end-capped were prepared from bisphenol A and4,4'-dichlorodiphenyl sulfone as described in Example 1.) The mechanicalproperties of the cured materials are similar. The environmentalstress-crack resistance and residual moduli at 200° C., however,improves with decreasing initial molecular weights of thepolysulfone-vinyl reactive resins; which is consistent with theanticipated direction of increasing cross-linking densities. Since thepolysulfone-vinyl reactive and the styrene monomer are miscible in allproportions, such a binder system can be a free-flowing powder, a dough,a paste or a solution depending on the relative amount of styreneincorporated. Preliminary data showed that in all instances a copolymercomposition was obtained. The glass transitional temperature of thelatter went down with increasing amount of polystyrene blocks in thecured resin. The glass transitional temperature values of copolymers at10, 17.4 and 30 percent polystyrene levels (calculated on the basis ofstyrene monomer used initially) were found to be 145°, 140°, and 130°C., respectively. Addition of divinyl benzene resulted in a higher Tgwith no apparent deleterious effect on the mechanical properties asshown in Table IX below.

                  TABLE IX                                                        ______________________________________                                        EFFECT OF THE INITIAL MOLECULAR WEIGHT OF                                     PSF-VR.sup.(a) TO THE PROPERTIES OF                                           PSF-VR.sup.(b) /STYRENE.sup.(c) BINDER SYSTEM.sup.(d)                         ______________________________________                                        PSF-VR.sup.(a), R.V. dl/gm                                                                      0.17     0.25     0.37                                      Tg °C.     140°                                                                            155°                                                                            145°                               Modulus at 200° C.                                                                       340      200      90                                        Tensile Strength, psi                                                                           10,400   10,000   10,400                                    Tensile Modulus × 10.sup.-6 psi                                                           2.99     2.84     2.76                                      Yield Elongation, %                                                                             --       --       5.5                                       Elongation at break,                                                                            8        5        7                                         Pendulum Impact, ft-lb/in.sup.3                                                                 34       15       15                                        ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl reactive, all have vinyl benzyloxy end groups.      .sup.(b) Polysulfonevinyl reactive.                                           .sup.(c) All formulations contained 17.4 percent by wt. of styrene            monomer.                                                                      .sup.(d) Cured by compression molding at 160° C.                  

EXAMPLE 15

Because mobility of the backbone is not restricted in apolysulfone-vinyl reactive resin/comonomer binder system at ambienttemperatures, it is readily cross-linked by electron-beam irradiation.(The hydroxy terminated polysulfones which were vinyl end-capped wereprepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as describedin Example 1.) Properties of some irradiated materials are summarized inTables X and XI below. Standard polysulfone (Union Carbide Corp.,P-1700) was found to undergo no apparent cross-linking, with or withoutthe comonomer additive, under the same conditions. MRAD is a radiationunit or Meg Rad; Rad is 100 ergs per gram.

                  TABLE X                                                         ______________________________________                                        PSF-VR.sup.(a) /COMONOMER BINDER SYSTEMS CURED BY                             ELECTRON BEAM IRRADIATION                                                     ______________________________________                                        PSF-VR.sup.(a), R.V.                                                                     0.21 (60).sup.(b)                                                                        0.35 (60)                                                                              0.35 (60)                                                                            0.35 (60)                               Comonomer.sup.(c)                                                                        NGD (30).sup.(b)                                                                         DB (30)  Styrene                                                                              DB (10)                                                                (40)                                                      Styrene    Styrene         Styrene                                            (10).sup.(b)                                                                             (10)            (30)                                    Radiation  20         20       20     20                                      Dose, MRAD.sup.(d)                                                            Gel Content, %                                                                           59         57       60     53                                      Color      Yellow     Light    Very   Light                                                         Yellow   Light  Yellow                                                                 Yellow                                         Transparency                                                                             Hazy       Slightly Clear  Slightly                                                      Hazy            Hazy                                    Mechanical Rigid,     Rigid,   Rigid, Rigid,                                  Strength   Brittle    Fairly   Fairly Fairly                                                        Brittle  Tough  Brittle                                 ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl radiation, endcapped with methacryloxy ethoxyl      groups.                                                                       .sup.(b) Percent by weight.                                                   .sup.(c) NGD = Neopentyl glycol diacrylate; DB = divinyl benzene.             .sup.(d) Unit for radiation dose.                                        

                  TABLE XI                                                        ______________________________________                                        EFFECT OF RADIATION DOSAGE ON THE CURING                                      OF PSF--VR/COMONOMER BINDER SYSTEM.sup.(a)                                    ______________________________________                                        Radiation Dosage,                                                                            5        10       15     20                                    MRad                                                                          Gel Content, %                                                                               54       65       67     64                                    Swelling Index.sup.(b)                                                                       3.48     2.93     2.92   3.3                                   Tg °C. 145°                                                                            155°                                                                            145°                                                                          150°                            Modulus at    690      600      670    570                                    300° C., psi                                                           ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl reactive, methacryloxy ethoxyl endgroups. 0.35      R.V. Comonomers, Neopentyl glycol diacrylate (30 percent); Styrene (10        percent).                                                                     .sup.(b) Corrected for extractables.                                     

Within the radiation dosage of 5 to 20 Mrad, there was found nosignificant difference in cross-linking densities of the irradiatedsamples. This is supported by experimental data shown in Table XI above,where the cross-linking density is expressed in terms of swelling indexand residual modulus at 300° C.

The polysulfone-vinyl reactive bearing the end reactive groups isnecessary for cross-linking. Polysulfone alone or with comonomer willnot crosslink without the vinyl reactive end groups.

The rather low degrees of cross-linking (up to 70 percent gel content)of the above irradiated samples is believed to be due to at leastpartially, an incomplete end-capping of the polysulfone-vinyl reactiveresins used. Spectroscopic data showed the soluble fraction beingentirely polysulfone; no polystyrene was detected.

EXAMPLE 16

When a photosensitizer is added, the polysulfone-vinylreactive/comonomer binder system becomes photo-curable; even thoughpolysulfone is known to be an U. V. absorbent. A polysulfone-vinylreactive film containing benzophenone and ethyl acrylate was irradiatedwith Linde U. V. curing equipment for different intervals, and theresults are summarized in Table XII below. (The hydroxy terminatedpolysulfones which were vinyl end-capped were prepared from bisphenol Aand 4,4'-dichlorodiphenyl sulfone as described in Example 1.)

                  TABLE XII                                                       ______________________________________                                        CURING OF PSF--VR/COMONOMER BINDER                                            SYSTEMS.sup.(a) BY U.V. IRRADIATION                                           ______________________________________                                        Irradiation                                                                               3          6         12                                           Dosage.sup.(b)                                                                Gel Content, %                                                                           18         27         50                                           Appearance clear, trans-                                                                            clear, trans-                                                                            clear, trans-                                           parent     parent     parent                                       Mechanical fairly tough                                                                             fairly tough                                                                             flexible, tough                              Strength                                                                      Resistance to                                                                            poor-fair  fairly good                                                                              good                                         Acetone-                                                                      Induced Stress                                                                Crack                                                                         ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl reactive, vinyl benzyloxy end groups, 0.37 R.V.     (80%); ethyl acrylate (19 percent); benzophenone (1 percent). U.V.            catalyst necessary when cured by U.V.                                         .sup.(b) Expressed in number of passes at a conveyor speed of 100 ft/min.

Because of the film thickness (about 10 mil) the degree of cross-linkingachieved was relatively low even after twelve passes. The partiallycured sample, however, was flexible, tough, and showed a significantimproyement in environmental stress crack resistance. Thus the use of acomonomer in conjunction with the polysulfone-vinyl reactive offers anumber of advantages: (1) to render the formulation curable byconventional methods; (2) to permit property modifications through awide selection of comonomers; and (3) to allow flexibility in meetingthe cost/performance requirements for different end-use areas.

EXAMPLE 17

Upon cross-linking, polysulfone-vinyl reactive resins exhibit a markedimprovement in environmental stress-crack resistance over the regularpolysulfone, similar to that of the polysulfone-silane reactive resins.The degree of improvement is usually parallel to the increase incross-linking density of the cured material. This effect is demonstratedclearly by the data shown in Table XIII below where the environmentalstress crack resistance of a series of cured polysulfone-vinyl reactivestyrene resins are related to their swelling indices. The cross-linkingdensity is expected to increase with a decrease in the initial molecularweight of the polysulfone-vinyl reactive, which is reflected by alowering in the swelling index. The environmental stress-crackresistance data was measured at constant stress levels using anenvironment of solvent-saturated cotton swab attached to the specimen.

                  Table XIII                                                      ______________________________________                                        ENVIRONMENTAL STRESS CRACK RESISTANCE                                         VS. CROSS-LINKING DENSITY                                                     ______________________________________                                        PSF--VR.sup.(a), R.V. (82).sup.(b)                                                              0.17     0.25      0.37                                     Comonomer (17).sup.(b)                                                                         styrene  styrene   styrene                                   Percent Extractables.sup.(c)                                                                    6.11     21.68    29.97                                     Swelling Index.sup.(d)                                                                          2.64     5.77      9.25                                     Time to Rupture:                                                              Toluene                                                                       1,000 psi        22 min.  --        10 sec.                                     500 psi        --       150 sec.  25 sec.                                   Trichloroethylene                                                             1,000 psi        15 min.  --        --                                          500 psi        --        7 min.    5 min.                                   Acetone                                                                       1,000 psi        25 min.  --        --                                          500 psi        --        75 sec.  20 sec.                                   ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl reactive, having vinyl benzyloxy end groups.        .sup.(b) Percent by weight.                                                   .sup.(c) Equals 100 minus percent gel.                                        .sup.(d) Corrected for extractables.                                     

EXAMPLE 18

The environmental stress-crack reistance of a cured polysulfone-vinylreactive comonomer composition aIso depended on the type and loading ofcomonomer employed. (The hydroxy terminated polysulfones which werevinyl end-capped were prepared from bisphenol A and 4,4'dichlorodiphenyl sulfone as described in Example 1.) Table XIV belowsets out the environmental stress-crack resistance performance, indecreasing order, of 20 different types of matrices in toluene andtrichloroethylene. Three of the more effective comonomers among thosestudied were divinyl benzene, acrylonitrile and styrene. The neatpolysulfone-vinyl reactive resin also performed well upon cross-linkingand is comparable to cross-linked polysulfone-silane reactive resin.When styrene was the comonomer used, the resistance of the curedmaterial to solvent-induced stress-crack deteriorated with increasingcomonomer loadings.

                                      TABLE XIV                                   __________________________________________________________________________    ENVIRONMENTAL STRESS CRACK RESISTANCE VS. COMONOMER TYPE                                              Toluene       Trichloroethylene                       Comonomer(s)                                                                              Percent                                                                              Swelling   Time to       Time to                           Type.sup.(a)                                                                              Extractables                                                                         Index.sup.(b)                                                                      Stress (psi)                                                                        Rupture (min)                                                                         Stress (psi)                                                                        Rupture (min)                     __________________________________________________________________________    Styrene (18.5)                                                                            3.9    1.70 2,000 >60     1,000 90                                Divinyl benzene (15.4)  4,000 4       4,000 7                                 None.sup.(c)                                                                              8.3    3.53 2,000 25      2,000 80                                Divinyl benzene (17.4)                                                                    13.5   2.78 1,000 >60     2,000 10                                                        2,000 18                                              Divinyl benzene.sup.(d) (17.4)                                                            3.5    1.96 2,000 5       2,000 14                                                                      4,000 1                                 Acrylonitrile (17.4)                                                                      3.5    2.38 1,000 >90     2,000 6                                                         2,000 5                                               Ethylene dimeth-                                                                          4.9    1.92 1,000 30      1,000 20                                acrylate (17.4)                                                               Styrene (9) 5.4    2.50 1,000 23      2,000 4                                                         2,000 3                                               Styrene (13.4).sup.(e)                                                                    5.3    2.72 2,000 2       1,000 5                                 Vinyl acetate (17.4)                                                                      8.2    2.73 1,000 22      1,000 11                                Ethyl acrylate (17.4)                                                                     8.1    2.79 1,000 10      1,000 16                                2-chloroethyl meth-                                                                       11.6   2.83 1,000 7       1,000 5                                 acrylate (17.4)                                                               Methyl methacrylate                                                                       8.8    3.15 1,000 5       1,000 6                                 (17.4)                                                                        2-Ethyl hexyl                                                                             8.2    3.08 1,000  41/2   1,000 6                                 acrylate (17.4)                                                               2-methyl Styrene                                                                          6.0    2.98 1,000 4       1,000 6                                 (17.4)                                                                        Diallyl isophthal-                                                                        8.2    2.54 1,000 4       1,000 5                                 ate (17.4)                                                                    Hydroxy propyl                                                                            11.0   2.96 1,000  31/2   1,000 5                                 Methacrylate (17.4)                                                           Styrene (29.4)                                                                            5.9    3.11 1,000 3       1,000 3                                 Ethyl Fumarate (17.4)                                                                     20.4   4.20 1,000  21/2   1,000 2                                 Trimethylol propane                                                                       8.2    2.15 1,000 1/2     1,000 3                                 trimethacrylate (17.4)                                                        PSF P-1700.sup.(f)                                                                        Soluble                                                                              --     200 Instantaneous                                                                           200 1/6                               __________________________________________________________________________     Notes:                                                                        .sup.(a) Percent by weight present in the feed before curing.                 .sup.(b) Corrected for extractables.                                          .sup.(c) Polysufonevinyl reactive, thermally cured at 275° C.          .sup.(d) Cured at 200°  C.                                             .sup.(e) Also contained 14.5 percent of a crosslinking booster.               .sup.(f) Polysulfone P1700 (union carbide)                               

EXAMPLE 19

The solution copolymerization of a polysulfone-vinyl reactive resin(acryloxy ethoxy end-groups, 0.23 initial R. V.) with styrene inmono-chlorobenzene was carried out to partial competition to minimizethe tendency of premature crosslinking. Nevertheless, when the weightpercent of PSF-VR in the feed exceeded 30 percent, complete gelationusually resulted. Between 12.5 and 30 percent polysulfone-vinyl reactiveloadings in the feed provided partially gelled products. Solublecopolymers were also prepared at polysulfone-vinyl reactive chargesbelow 12.5 percent. The characteristics of some of the solublecopolymers are shown in Table XV below. Compositions of these copolymerswere determined by elemental analysis. In every instance thepolysulfone-vinyl reactive was found to be richer in the copolymer thanin the feed. They are soluble in methyl ethyl ketone or toluene, whichare non-solvents for the polysulfone-vinyl reactive homopolymers. Themolecular weights of the products increased rapidly with increasingpolysulfone-vinyl reactive/styrene charge ratios. These thermoplasticresins can be compression-molded to clear or slightly hazy plaques; theyare usually brittle and resemble polystyrene.

Any advantage of raising the glass transition temperature of polystyreneby copolymerizing with polysulfone-vinyl reactive was found to be minor.Preliminary DSC data showed that the glass transition temperature of thecopolymers increased only slightly from that of polystyrene (Tg 100° C.)at these levels of polysulfone-vinyl reactive contents; substantialincreases were achieved only at high loadings of polysulfone-vinylreactive component.

                  TABLE XV                                                        ______________________________________                                        SOLUTION COPOLYMERIZATION OF                                                  PSF-VR.sup.(a) WITH STYRENE                                                   ______________________________________                                        PSF-VR.sup. (a) /styrene                                                                     0/100   5/95    7.5/ 10/90 12.5/                               Wt. ratio in feed              92.5       87.5                                PSF-VR.sup. (a) /polystyrene.sup.(b)                                                         0/10    9.27/   16.4/                                                                              14.9/ 24.7/                               Wt. ratio in copolymer 90.73   83.6 85.1  75.3                                R.V., dl/gm.sup.(c)                                                                          0.51    0.58    0.61 0.70  1.06                                Conversion, percent                                                                          48      49      48   55    50                                  ______________________________________                                         Notes:                                                                        .sup.(a) Polysulfonevinyl reactive, acryloxy ethoxy endgroups, 0.23 R.V.      .sup.(b) Copolymer composition determined by elemental analysis.              .sup.(c) Measured in chloroform at 25° C.                         

EXAMPLE 20

Several glass mat reinforced polysulfone-vinyl reactive laminates wereprepared.

(The hydroxy terminated polysulfones which were vinyl end-capped wereprepared from bisphenol A and 4,4'-dichlorodiphenyl sulfone as describedin Example 1.) The mechanical properties of two of the glass matreinforced polysulfone-vinyl reactive laminates were compared to thoseof a laminate formulated with a commercial corrosion-resistant polyesterresin (ICI Atlac 382--05A)--the results are given in Table XVI below. Inaddition to their good mechanical strength, the finished laminates alsoexhibited a high gloss and smooth surface comparable to the commercialmaterial. A very high heat deflection temperature was obtained with thelaminate made from the vinyl benzyloxy end-capped, 0.17 R. V.polysulfone-vinyl reactive resin (which may be the result of a highercross-linking density attained with this particular resin).

The electrical properties of one of the glass mat reinforcedpolysulfone-vinyl reactive laminate are listed in Table XVII belowtogether with those of a laminate made with a commercial polyester resin(Freeman Stypol-2995). Performance of both matrix resins are ratedexcellent.

                  TABLE XVI                                                       ______________________________________                                        MECHANICAL PROPERTIES OF GLASS                                                MAT.sup.(a) REINFORCED LAMINATES                                                           PSF-VR.sup. (c)                                                               (Vinyl    PSF-VR.sup. (c)                                                     benzyloxy (Methacryloxy                                                                             Atlac                                      Matrix Resin.sup.(b)                                                                       0.17)     ethoxy 0.21)                                                                              382-05A                                    ______________________________________                                        Percent Glass (plies)                                                                      29        30          28                                         Sp. gr.      1.82      1.85        1.81                                       Tensile Strength, psi                                                                      14,300    14,400      11,900                                     Tensile Modulus, ×                                                                   1.01      0.89        0.83                                       10.sup.-6 psi                                                                 Elongation, percent                                                                        1.69      1.79        1.81                                       Flexural Strength psi                                                                      24,700    28,700      27,600                                     Flexural Modulus, ×                                                                  1.48      1.38        1.55                                       10.sup.-6 psi                                                                 Izod Impact Strength                                                                       13.5      15.0        13.9                                       ft-lb/in. of notch                                                            Compressive Strength,                                                                      15,900    14,000      14,100                                     psi                                                                           Compressive Modulus,                                                                       1.98      1.96        1.60                                       10.sup.-6 psi ×                                                         HDT @ 264 psi, °C.                                                                  276°-305°                                                                 258° 258°                                                       (6 mil. def.)                                                                             (2 mil. def.)                              ______________________________________                                         Notes:                                                                        .sup.(a) VitroFlex 630D, 1 inch chopped strand mat.                           .sup.(b) Dissolved in styrene monomer.                                        .sup.(c) Polysulfonevinyl reactive.                                      

                  TABLE XVII                                                      ______________________________________                                        ELECTRICAL PROPERTIES OF GLASS                                                MAT.sup.(a) REINFORCED LAMINATES                                                               PSF-VR.sup. (c)                                                               Methacryloxy                                                                  Ethoxy (end groups,                                                                         Freeman                                        Matrix Resin.sup.(b)                                                                           0.20 R.V.)    Stypol 2995                                    ______________________________________                                        Percent Glass (plies)                                                                          28 (4)        28 (4)                                         Dielectric Strength, volts/mil                                                                 359           194                                            Volume Resistivity,                                                                            0.6           1.1                                            Ohm-cm × 10.sup.-16                                                     Dissipation Factor, 60 cycles                                                                  0.00325       0.00599                                        10.sup.3 cycles  0.00283       0.00579                                        Dielectric Constant, 60 cycles                                                                 4.90          5.63                                           10.sup.3 cycles  4.88          5.56                                           Arc Resistance, sec.                                                                           167           182                                            ______________________________________                                         Notes:                                                                        .sup.(a) VitroFlex 630D, 1 inch chopped strand mat.                           .sup.(b) Dissolved in styrene monomer.                                        .sup.(c) Polysulfonevinyl reactive.                                      

Examples 21 and 22 involve the cross-linking of the polysulfone-vinylreactive resins.

EXAMPLE 21

A methacryloxy ethoxy end-capped polysulfone-vinyl reactive resin havinga reduced viscosity (R.V.) of 0.22 dl/g (measured in chloroform at 25°C.) and a number average molecular weight of 11,590 was treatedthermally in the presence of dicumyl peroxide to produce a highermolecular weight polymer of a cured polymer composition. (The hydroxyterminated polysulfones which were vinyl end-capped were prepared frombisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example1.) Table XVIII sets out the data.

                                      TABLE XVIII                                 __________________________________________________________________________                      Dicumyl Proxide.sup.(a)                                     Method     T °C.                                                                      t.sub.min                                                                        % of wt.  Results                                           __________________________________________________________________________    Compression molding                                                                      190°                                                                       30 2         R.V. advanced to 0.65 dl/g                        Compression molding                                                                      220°                                                                       10 2         Cross-linked no                                                               longer soluble in CHCl.sub.3                      Compression molding                                                                      190°                                                                       30 2% plus   Cross-linked, no                                                    1% TAC.sup.(b)                                                                          longer soluble in CHCl.sub.3                      Compression molding                                                                      (i)190°                                                                    (i)30                                                                            2% plus   Highly cross-lined                                           (ii)220°                                                                   (ii)12                                                                           1% TAC    no longer soluble in CHCL.sub.3                   __________________________________________________________________________     Notes:                                                                        .sup.(a) Incorporated by imbibing from hexane solution and followed by        vacuum drying to remove the hexane.                                           .sup.(b) Triallylcyanurate, a crosslinking booster.                      

EXAMPLE 22

A vinyl benzyloxy end-capped polysulfone-vinyl reactive resin having aR. V. of 0.37 dl/g (measured in chloroform at 25° C. was compressionmolded at elevated temperatures in the presence of a radical initiatorto produce a cross-linked polyarylether composition. (The hydroxyterminated polysulfones which were vinyl end-capped were prepared frombisphenol A and 4,4'-dichlorodiphenyl sulfone as described in Example1.) Table XIX sets out the data.

                                      TABLE XIX                                   __________________________________________________________________________                 Initiator Loading                                                                      Molding                                                 Initiator Type                                                                             % by wt  T ° C.                                                                     t min                                                                            Results                                          __________________________________________________________________________    Dicumyl peroxide                                                                           1        220°                                                                       10 crosslinked, no                                                               longer soluble in CHCl.sub.3                     Dicumyl peroxide                                                                           1        220°                                                                       10 crosslinked, improved                            TAC.sup.(a)  1               stress-cracking                                                               resistance to acetone                            Vinyltris (t-butyl-peroxy)                                                                 1        220°                                                                       10 crosslinked, good                                silane                       adhesion to                                                                   aluminum substrate                               2,5-Dimethyl-2,5-bis                                                                       1        220°                                                                       10 crosslinked, improved                            (t-butylperoxy)hexyne-3      stress-cracking                                                               resistance.                                      __________________________________________________________________________     Notes:                                                                        .sup.(a) Triallyl cyanurate                                              

EXAMPLE 23

Into a 500 ml 3-necked flask, fitted with a water trap, mechanicalstirrer, condenser, thermometer and an argon inlet, there was placed 20gm (0.0036 mole) of a hydroxy-terminated sulfone oligomer (molecularweight =5,580) and 100 ml of dimethyl sulfoxide. (The hydroxy terminatedpolysulfone was prepared from bisphenol A and 4,4 'dichlorodiphenylsulfone as described in Example 1.) The mixture was heated to 90° C. togive a homogeneous solution. Thereafter, 1 ml of a NaOH solution (28.8percent, equivalent to 0.0072 mole) was introduced together with 25 mlof benzene. Azeotropic distillation began at about 115° C. and wasallowed to continue until no more water was forming. A total of 2 mlwater was collected. The reaction vessel temperature was raised to 135°C. and a solution of 3.8 g of allyl chloride (0.05 mole) in 5 ml ofdimethyl sulfoxide was added. The reaction medium turned to a lightamber color and the solution was kept at a temperature between 125° to130° C. for a period of 45 minutes. Upon cooling to room temperature,the salt was removed by filtration. The filtrate was poured into a largeexcess of isopropanol and a white fluffy solid was recovered. Theconversion was better than 98 percent (19.7 g). It showed a reducedviscosity of 0.18 dl/g in chloroform at 25° C. Infrared spectrum of afilm cast from CHCl₃ indicated that the resulting sulfone oligomers nolonger possessed hydroxy end-groups. The product was an alloxy(allyloxy) end-capped polysulfone-vinyl reactive resin (oligomer).

EXAMPLE 24

Using the same apparatus as described in Example 23 but employing thefollowing starting materials and reagents.

    ______________________________________                                        Hydroxy terminated polysulfone                                                                     39 gm (0.001 mole)                                       (molecular wt. 39,000)                                                        KOH (in the form of a 11.2%                                                                        0.112 gm (0.002 mole)                                    solution)                                                                     Dimethyl Sulfoxide   200 ml                                                   Benzene               80 ml                                                   Allyl Chloride       1.147 gm (0.015 mole)                                    ______________________________________                                    

(The hydroxy terminated polysulfone was prepared from bisphenol A and4,4'-dichlorodiphenyl sulfone as described in Example 1.) Theend-capping reaction and product isolation were carried out followingthe procedures used in Example 23. 38 g of a white fluffypolysulfone-vinyl reactive polymer was recovered. It showed a reducedviscosity of 0.58 dl/gm in chloroform at 25° C.

EXAMPLE 25

Ten grams of the alloxy end-capped polysulfone resin prepared in Example23 was placed between two sheets of aluminum foil and the assembly waspressed at 240° C. for a period of 15 minutes. T-peel test showed thepeel strength between the aluminum foil and polysulfone to be between 4to 8 lbs./in.

EXAMPLE 26

A solution of 0.1 gm of each of 2,5-dimethyl-2,5-bis-(trimethylsilylperoxy)-hexane and triallylcyanaurate in hexane wasintimately blended with 5 gm of the alloxy end-capped sulfone oligomerprepared in Example 23. Upon being intimately blended, the hexane wasremoved under vacuum at 50° C. The dried blend was molded with anelectrically-heated hydraulic press at 240 ° C. for a 15 minute cycle.The resulting plaque was partially soluble in chloroform, and thepresence of cross-linked gels was visible.

EXAMPLE 27

An aluminum-polysulfone-aluminum joint was prepared with the alloxyterminated polysulfone resin prepared in Example 23 and aluminumQ-panels. The polysulfone-vinyl reactive resin adhesive layer was curedby adding 2 percent of each of2,5-dimethyl-2,5-bis-(trimethyl-silylperoxy) hexane andtriallylcyanurate in a manner as described in Example 26. The finishedjoint was measured for T-peel strength with an Instron machine at across-head speed of 2 inches per minute. The value was 5 to 6 lbs./in.Under similar conditions, joints made of standard polysulfone showedless than 2 lbs./in. peel strength.

EXAMPLE 28

Alloxy terminated polysulfone resin prepared from Example 23 was moldedat 210° C. to a 25 mil thick plaque. A set of lap-shear joints wassubsequently made with the above plaque and titanium bars (1"×4"×55mil). A peroxide initiator, vinyl tris-(t-butylperoxy) silane, was usedto prime the surface of both the polysulfone-vinyl reactive resin layerand the titanium substrates. Curing was effected at 230° C. for a tenminute cycle. Lap-shear strength of the above joints was measured to be880 psi.

EXAMPLE 29

Into a 2 liter, four-necked flask, equipped with a mechanical stirrer,water trap, addition funnel, thermometer and argon inlet, there wasplaced 174.62 grams (0.8 mole) of 4,4'-thiodiphenol, 500 milliliters ofDMSO, and 700 milliliters of monochlorobenzene. Upon dissolution at 75°C., a caustic solution containing 64.96 grams (98.5 percent purity) ofNaOH and 75 milliliters of distilled water was introduced. Azeotropicdistillation was carried out until no more water was produced. A hot,dry monochlorobenzene solution containing 215.95 grams (0.753 mole) of4,4'-dichlorodiphenyl sulfone was introduced. The polymerizationreaction was maintained at 165° C. for 90 minutes. Thereafter, thesodium phenolate end-group concentration was determined by titration.The polymer had the following structural formula: ##STR23## The polymerwas end-capped with allyl groups via the sodium phenolate end groupsfollowing the procedure of Example 1 using allyl chloride.

EXAMPLE 30

Into a 2 liter, four-necked flask, equipped with a mechanical stirrer,water trap, addition funnel, thermometer, and argon inlet, there wasplaced 74.49 grams (0.4 mole) of p,p'-biphenol, 350 milliliters ofmonochlorobenzene and 275 milliliters of DMSO. Upon dissolution at 70°C., a caustic solution containing 32.48 grams of NaOH (98.5 percentpurity) and 37.5 milliliters of distilled water was added. Azeotropicdistillation was carried out until the reaction medium temperaturereached 155° C., when a total of 382.5 grams of distillate had beencollected. The temperature was lowered to 140° C. and a hot solution of109.05 grams (0.38 mole) of sulfone monomer in 125 milliliters of drymonochlorobenzene was rapidly introduced. Thereafter, the reactiontemperature was raised to 165° C. by distilling off 162.2 grams ofmonochlorobenzene and maintained at this temperature overnight. Thesodium phenolate end-groups were determined by titration. The polymerhad the following structural formula: ##STR24## The polymer wasend-capped with vinyl benzyl groups via the sodium phenolate end groupsfollowing the procedure of Example 2 using vinyl benzyl chloride.

EXAMPLE 31

Into a 1-liter, four-necked flask, equipped with a mechanical stirrer,water trap, addition funnel, thermometer and argon inlet, there wasplaced 101.12 grams (0.4 mole) of 4,4'-sulfonyl-diphenol, 510milliliters of monochlorobenzene and 250 milliliters of DMSO. Upondissolution at 75° C., a caustic solution containing 16.24 grams (98.5percent purity, 0.8 mole) of sodium hydroxide and 37.5 milliliters ofdistilled water was introduced. Azeotropic distillation was carried outuntil the temperature of the reaction medium reached 155° C. when atotal of 290.4 grams of distillate was collected. The reactiontemperature was lowered to 140° C. and a hot solution of 97.55 grams(0.34 mole) of sulfone monomer in 12 milliliters of drymonochlorobenzene was added. An additional 441.8 grams of solvent wasdistilled off to raise the reaction temperature to 165° C. It was keptat this temperature for 3 hours. The polymer had the followingstructural formula: ##STR25## The polymer was end-capped with vinylbenzyl groups via the sodium phenolate end groups following theprocedure of Example 2 using vinyl benzyl chloride.

EXAMPLE 32

Into a 500 cc four-neck flask fitted with stirrer, thermometer, droppingfunnel, and Y tube with N₂ inlet tube and helices-packed fractionatingcolumn with water trap and condenser, were placed 22.83 grams ofBisphenol-A (0.1 mole), 45 milliliters of DMSO and 55 milliliters oftoluene. Air was displaced by nitrogen and 16.02 grams of 49.94 percentNaOH (0.2 mole) was added. The mixture was refluxed, removing wateruntil no more was evident; then toluene was distilled off to a pottemperature of 160° C. The polymer was end-capped with allyl groups viathe sodium phenolate end groups following the procedure of Example 1using allyl chloride.

EXAMPLE 33

The same apparatus and procedure as in Example 32 was used with 25.03grams of 4,4'-dihydroxydiphenyl sulfone (0.1 mole), 60 milliliters ofDMSO, 85 milliliters of toluene and 16.04 grams of 49.90 per cent NaOH(0.2 mole). The bisphenol disodium salt was dehydrated as before andmost of the toluene was distilled. The mixture was cooled. The polymerderived from bisphenol S was end-capped with allyl groups via the sodiumphenolate end groups following the procedure of Example 1 using allylchloride.

EXAMPLE 34

Into an apparatus similar to that described in Example 32 were placed25.03 grams of 4,4'-dihydroxydiphenyl sulfone (0.1 mole), 70 millilitersof DMSO and 100 milliliters of toluene. Air was displaced by N₂ and16.03 grams of 49.90 percent NaOH (0.2 mole) was added. The mixture wasrefluxed, removing water until no more was evident, and then toluene wasdistilled off to a pot temperature of 160° C. A solution of 24.15 gramsof 4,4'-difluorodiphenyl sulfone (0.095 mole) and 33 milliliters of drychlorobenzene were added. The mixture was heated with stirring at 160°to 170° C. for 21/2 hours to complete the oligomerization and thencooled to 130° C. The polymer (Bisphenol S polyether) was end-cappedwith vinyl benzyl groups via the sodium phenolate end groups followingthe procedure of Example 2 using vinyl benzyl chloride.

EXAMPLE 35

Into an apparatus like that described in Example 32 were placed 22.83grams of Bisphenol A (0.1 mole), 70 milliliters of DMSO and 80milliliters of toluene. Air was displaced by nitrogen and 15 85 grams of50.48 percent NaOH (0.2 mole) was added. The mixture was refluxed,removing water until no more was evident, and then toluene was distilledoff to a pot temperature of 150° C. A solution of 20.51 grams of4,4'-difluorobenzophenone (0.095 mole) in 20 milliliters of drychlorobenzene was gradually added. On adding the last increment of thedifluorobenzophenone, the polymer viscosity became very high, but oncontinued heating at about 160° C. for 11/2 hours it decreased somewhat.The mixture was diluted with dry monochlorobenzene and cooled to about140° C. The polymer (Bisphenol--difluorobenzophenone polyether) wasend-capped with vinyl benzyl groups via the sodium phenolate end groupsfollowing the procedure of Example 2 using vinyl benzyl chloride.

EXAMPLE 36

Into a 250 ml. flask equipped with a stirrer, thermometer, a watercooled condenser and a Dean Stark moisture trap filled with benzene,there were placed 11.42 grams of 2,2-bis-(4-hydroxyphenyl)propane (0.05moles), 13.1 grams of 42.8 percent potassium hydroxide solution (0.1moles KOH), 50 ml. of dimethylsulfoxide and 6 ml. benzene and the systempurged with nitrogen to maintain an inert atmosphere over the reactionmixture. The mixture was refluxed for 3 to 4 hours, continuouslyremoving the water contained in the reaction mixture as an azeotropewith benzene and distilling off enough of the latter to give a refluxingmixture at 130° to 135° C., consisting of the dipotassium salt of the2,2-bis(4-hydroxyphenyl)propane and dimethylsulfoxide essentially freeof water. The mixture was cooled and 14.35 grams (0.05 mole) of4,4'-dichlorodiphenylsulfone was added followed by 40 ml. of anhydrousdimethylsulfoxide, all under nitrogen pressure. The mixture was heatedto 130° C. and held at 130° to 140° C. with good stirring for 4 to 5hours. The viscous, orange solution was poured into 300 ml. water, andrapidly circulating in a Waring Blender. The resultant finely dividedwhite polymer was filtered and then dried in a vacuum oven at 110° C.for 16 hours. The yield was 22.2 g (100 percent) and the reaction was 99percent complete based on a titration for residual base. The polymer hadthe following structural formula: ##STR26## The polymer was end-cappedwith allyl groups via the potassium phenolate end groups following theprocedure of Example 1 using allyl chloride.

EXAMPLE 37

This example was conducted using the procedure of Example 36, except1,1-bis-(4-hydroxyphenyl)-1-phenylethane (bisphenol of acetophenone) wasused as the dihydric phenol. The reaction time was 10 hours at 130° to140° C. and the reduced viscosity in chloroform was 0.54. At theconclusion of the reaction, a solution of 0.5 g methyl chloride in 6 mlof dimethylsulfoxide was added at 90° to 100° C. to convert unreactedaryloxide end-groups to the more stable aryl methyl ether end-groups.The polymer had the following structural formula: ##STR27## The polymerwas end-capped with vinyl benzyl groups via the sodium phenolate endgroups following the procedure of Example 2 using vinyl benzyl chloride.

EXAMPLE 38

This example was conducted using the procedure of Example 36, exceptthat the dihydric phenol employed was 4,4'-dihydroxydiphenylmethane andthe reaction temperature and time were 130° to 135° C. and 7 hours,respectively. The polymer had the following structural formula:##STR28## The polymer was end-capped with vinyl benzyl groups via thesodium phenolate end groups following the procedure of Example 1 usingvinyl benzyl chloride.

EXAMPLE 39

This example was conducted using the procedure of Example 36, excepthydroquinone was used as the dihydric phenol and reaction conducted at130° to 140° C. for 6 hours. The polymer had the following structuralformula: ##STR29## The polymer was end-capped with allyl groups via thesodium phenolate end groups following the procedure of Example 1 usingallyl chloride.

EXAMPLE 40

This example was conducted using the procedure of Example 36, exceptthat 1,3-bis(p-hydroxyphenyl)-1-ethylcyclohexane (the bisphenol preparedby acid catalyzed condensation of 2 moles of phenol with one molevinylcyclohexene) was used as the dihydric phenol. The reaction wasconducted for 7 hours at 130° to 140° C. The polymer had the followingstructural formula: ##STR30## The polymer was end-capped with allylgroups via the sodium phenolate end groups following the procedure ofExample 1 using allyl chloride.

EXAMPLE 41

This example was conducted using the procedure of Example 36, exceptthat the dihydric phenol was 1,1-bis(4-hydroxyphenyl)-2,2-dimethylethane(i.e., the bisphenol of isobutyraldehyde). The reaction was conductedfor 7 hours at 130° to 135° C. The polymer had the following structuralformula: ##STR31## The polymer was end-capped with allyl groups via thesodium phenolate end groups following the procedure of Example 1 usingallyl chloride.

EXAMPLE 42

This example was conducted using the procedure of Example 36, exceptthat the dihydric phenol was 4,4'-dihydroxybenzophenone. The reactionwas conducted for 41/2 hours at 135° to 145° C. The polymer had thefollowing structural formula: ##STR32## The polymer was end-capped withallyl groups via the sodium phenolate end groups following the procedureof Example 1 using allyl chloride.

EXAMPLE 43

This example was conducted using the procedure of Example 36, except thedihydric phenol was 4,4'-(dihydroxyphenyl) diphenylmethane (bisphenol ofbenzophenone). The reaction was conducted for 20 minutes at 110°-127° C.The polymer had the following structural formula: ##STR33## The polymerwas end-capped with vinyl benzyl groups via the sodium phenolate endgroups following the procedure of Example 2 using vinyl benzyl chloride.

EXAMPLE 44

To a solution of 24.26 g of 4,4'-dihydroxy diphenyl ether (0.12 mole) in160 cc. of dimethyl sulfoxide and 45 cc. benzene in a 500 cc. reactionflask was added under a nitrogen atmosphere 25.27 g of 53.28 percent KOH(0.24 mole). The mixture was refluxed with stirring and slow nitrogensparge with removal of water by a Dean-Stark trap for a total of 5 hrs.The mixture of solid potassium salt of 4,4'-dihydroxydiphenyl ether andsolvent was cooled to room temperature and 34.46 g of4,4'-dichlorodiphenylsulfone (0.12 mole) added. The reaction mixture wasthen warmed to about 130° C. for 3.5 hours during which time it becamequite viscous. The mixture was cooled to 110° to 120° C. and methylchloride bubbled in for a short time to methylate any unreactedphenoxide groups. The polymer had the following structural formula:##STR34## The polymer was end-capped with allyl groups via the potassiumphenolate end groups following the procedure of Example 1 using allylchloride.

EXAMPLE 45

To a solution of 27.4 g of 2,2-bis(4-hydroxyphenyl)propane (0.12 mole),160 cc. of dimethylsulfoxide and 45 cc. of benzene there was added 25.27grams of a 53.28 percent aqueous KOH solution 0.24 mole). The mixturewas refluxed as in Example 44 for 5 hours for water removal and securingthe anhydrous dipotassium salt of the 2,2-bis(4-hydroxyphenyl) propanedissolved in the dimethylsulfoxide. The mixture was cooled and 23.04 gof 2,4-dichloronitrobenzene (0.12 mole) was added. Some darkening and arapid temperature rise to 70° C. were noted. After about 10 min. at thistemperature, the viscosity was noticeably increased. The mixture washeld for 31/2 hours at about 80° C. and then methyl chloride bubbled infor a short time. The reaction mixture was diluted with 40 cc. benzeneand filtered through a Seitz filter to remove salt. The polymer had thefollowing structural formula: ##STR35## The polymer was end-capped withvinyl benzyl groups via the potassium phenolate end groups following theprocedure of Example 5 using vinyl benzyl chloride.

EXAMPLE 46

This example was conducted using essentially the procedure of Example29, employing as one reactant, the dipotassium salt ofhexafluorobisphenol-A having the structural formula: ##STR36## Thepolymer was end-capped with vinyl benzyl groups via the potrassiumphenolate end groups following the procedure of Example 2 using vinylbenzyl chloride.

EXAMPLE 47

This example was conducted using substantially the procedure of Example46, except that 4,4'-difluorobenzophenone was substituted for the4,4'-difluorodiphenylsulfone. The polymer had the following structuralformula: ##STR37## The polymer was end-capped with vinyl benzyl groupsvia the potassium phenolate end groups following the procedure ofExample 2 using vinyl benzyl chloride.

EXAMPLE 48

Into an air-free 500 ml flask equipped with a stirrer, gas inlet tube,thermocouple, distillation trap and reflux condenser was placed 65 gramsof dimethylsulfoxide and 200 grams of chlorobenzene azeotrope former.The ratio of dimethylsulfoxide to chlorobenzene was 1:3.1. 39.1 grams(0.1314 mole) of 1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane (thebisphenol prepared by an acid catalyzed condensation of 2 moles ofphenol with one mole vinylcyclohexene) and 37.7 grams (0.1314 mole) of4,4'-dichlorodiphenylsulfone were then simultaneously charged into thereaction flask which was immediately sparged with nitrogen to excludeany possibility of air contamination. Thereafter, the solution washeated to about 75° C. and 21.5 grams (0.2628 mole) of 49 percentaqueous sodium hydroxide were added from a dropping funnel. Two liquidphases formed immediately. The reaction mass was then heated to 120° C.at which point a water-chlorobenzene azeotrope began distilling from thesystem. Distillation of the azeotrope was continued for about 30 minuteswith a gradual rise in temperature to 140° C. at which point essentiallyall of the water in the system was removed. The disodium salt of the1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane precipitated and one liquidphase was present. Excess chlorobenzene was then removed by increasingthe temperature gradually to about 170° C. and distilling off excessazeotrope former for about 20 minutes. At this point the ratio ofdimethylsulfoxide to chlorobenzene was 4:1. As soon as this ratio wasreached, considerable polymerization occurred because of the highreaction temperature. The temperature of the reaction mass was rapidlydropped to about 150° to 160° C. and held there with stirring for aboutone hour. Gaseous methyl chloride was introduced until no more wasabsorbed. The mixture was diluted to 10 to 15 percent solids by addingchlorobenzene. The polymer ha the structural formula: ##STR38## Thepolymer was end-capped with vinyl benzyl groups via the sodium phenolateend groups following the procedure of Example 2 using vinyl benzylchloride.

EXAMPLE 49

Example 48 was repeated except that in place of4,4'-dichlorodiphenylsulfone, 32.0 g (0.1314 mole) of4,4'-dichloroazobenzene was used. The polymer had the followingstructural formula: ##STR39## The polymer was end-capped with allylgroups via the sodium phenolate end groups following the procedure ofExample 1 using allyl chloride.

EXAMPLE 50

Example 48 was repeated except that in place of the1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane, 25.5 g (0.05 mole) oftetramethylene dibisphenol-A (the bisphenol prepared by condensation of2 moles of phenol with 1,4-bis(p-isopropenyl phenyl) butane and thecorresponding molecular quantities of the 4,4'-dichlorodiphenyl sulfone(14 4 g, 0.05 mole) and caustic (8.1 g of 12.46 me/g., 0.10 mole) wereused. The polymer had the following structure: ##STR40## The polymer wasend-capped with allyl groups via the sodium phenolate end groupsfollowing the procedure of Example 1 using allyl chloride.

EXAMPLE 51

Example 48 was repeated except that instead of the1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane, 22.5 g (0.0985 mole) ofbisphenol A was used in addition to 16.8 g (0.0329 mole oftetramethylene dibisphenol A. The polymer had the structural formula:##STR41## The polymer was end-capped with vinyl benzyl groups via thesodium phenolate end groups following the procedure of Example 2 usingvinyl benzyl chloride.

EXAMPLE 52

Example 48 was repeated except that instead of the1,3-bis-(p-hydroxyphenyl)-1-ethylcyclohexane, 22.5 g (0.0985 mole) ofbisphenol A was used in addition to 6.7 g (0.033 mole) of4,4'-dihydroxydiphenyl ether. The polymer had the structural formula:##STR42## The polymer was end-capped with vinyl benzyl groups via thesodium phenolate end groups following the procedure of Example 2 usingvinyl benzyl chloride.

EXAMPLE 53

Example 48 was repeated except that in place of4,4'-dichlorodiphenylsolfone, 61.17 g of1,4-bis(p-chloro-N-methyl-benzene sulfonamido)butane, having thestructural formula: ##STR43## (melting point 179.5°-180.5° C.) andprepared by the reaction of potassiump-chloro-N-methyl-benzenesulfonamide with 1,4-dichlorobutane, was used.The reaction time was 2 hours at about 160° C. The polymer had thestructural formula: ##STR44## The polymer was end-capped with allylgroups via the sodium phenolate end groups following the procedure ofExample 1 using allyl chloride.

EXAMPLE 54

Example 48 was repeated except that in place of4,4'-dichlorodiphenylsulfone, 57.2 g of piperazinebis-p-chlorobenzenesulfonamide having the structural formula: ##STR45##(melting point 324° to 325° C.) and prepared by reactingp-chloro-benzenesulfonyl) chloride with piperazine, was used. Thepolymerization time was 1 hour at 160° to 170° C. The polymercrystallized out on cooling the reaction mixture. The polymer had thestructural formula: ##STR46## The polymer was end-capped with allylgroups via the sodium phenolate end groups following the procedure ofExample 1 using allyl chloride.

EXAMPLE 55

A 50/50 blend of the polysulfone-vinyl reactive resin of Example 1 and acommercial polysulfone was extruded with a 1-foot single-screw extruderoperating at a temperature between 260° to 310° C., and was pelletizedto give a uniform composition. The pellets were injection molded using aVan Dorne Injection Machine at 358° C. The barrel residence time wasabout 3 minutes, and the mold temperature was maintained at 115° C. Theinjection-molded parts were post-cured using either an air oven or anacid (or base) bath. For instance, a 21/2"×1/2"×1/8" specimen was heatedin an air oven at 275° C. for a period of 35 minutes.

EXAMPLE 56

The polysulfone-vinyl reactive resin (of Example 3) was compressionmolded at 220° C. (200 psi, 30 min.) to form a 20 mil thick plaque. Thelatter was laminated with a 4"×1"×1/16" titanium panel at an initialtemperature of 220° C. and a finish temperature of 270° C. The totalheating time lasted for 55 min., and only contact pressure was used.

What is claimed is:
 1. A thermosetting, end-capped, polyarylenepolyether having the formula:

    Z--O--(polyarylene polyether)--O--Z'

wherein Z and Z' are each polymerizable, ethylenically-unsaturatedradicals selected from the group consisting of allyl, vinyl,vinylbenzyl, vinyloxyethylene, acrylate, oxyethylene acrylate,oxyethylene methacrylate and methacrylate radicals.
 2. The end-cappedpolyarylene polyether of claim 1 wherein said --(polyarylenepolyether)--structural unit comprises:

    --E--(OE'--O--E)n--

wherein n is a positive integer, E is the residuum of a dihydric phenoland E' is the residuum of an aromatic compound having two halosubstituents.
 3. The end-capped polyarylene polyether as claimed inclaim 2 wherein n is 2 to
 300. 4. The end-capped polyarylene polyetherof claim 2 wherein E is selected from the group consisting of ##STR47##and mixtures thereof wherein x is selected from the group --CO--, --SO₂--, --CR,R'-- a direct bond, --O--, --S-- and C₁ -C₆ alkyl, R and R' areindependently H-- or C₁ -C₆ alkyl; and E' comprises at least one memberof the group ##STR48## wherein Y is --SO₂ --, --CO--, or C₁ -C₄perfluoroalkyl.
 5. The end-capped polyarylene polyether of claim 2wherein E is selected from the group consisting of ##STR49## andmixtures thereof and E' is selected from the group consisting of##STR50## and mixtures thereof.
 6. The end-capped polyarylene polyetherof claim 1 wherein Z and Z' are vinyl benzyl groups.
 7. The end-cappedpolyarylene polyether of claim 1 wherein Z and Z' are allyl groups.
 8. Athermosetting, end-capped polyarylene polyether having the formula##STR51## wherein n is from 2 to 200, and Z is selected from the groupallyl, vinyl, vinyloxyethylene, vinyl benzyl, oxyethylene acrylate,oxyethylene methacrylate, acrylate and methacrylate.
 9. A polymerizablemixture comprising at least one polymerizable, ethylenically-unsaturatedmonomer and the thermosetting, end-capped polyarylene ether of claim 1.10. The mixture of claim 9 wherein the ethylenically-unsaturated monomeris selected from the group consisting of acrylate monomers, methacrylatemonomers, vinyl aromatic monomers, acrylonitrile monomers, allylmonomers, conjugated diene monomers, and mixtures thereof.